WO2004092185A1 - Luminescent lanthanide (iii) -chelated dendritic complexes having light-harvesting effect and their synthetic methods - Google Patents

Luminescent lanthanide (iii) -chelated dendritic complexes having light-harvesting effect and their synthetic methods Download PDF

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WO2004092185A1
WO2004092185A1 PCT/KR2004/000181 KR2004000181W WO2004092185A1 WO 2004092185 A1 WO2004092185 A1 WO 2004092185A1 KR 2004000181 W KR2004000181 W KR 2004000181W WO 2004092185 A1 WO2004092185 A1 WO 2004092185A1
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Prior art keywords
porphyrin
coo
phenyl
terpyridine
solid state
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PCT/KR2004/000181
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French (fr)
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Hwan-Kyu Kim
Soo-Gyun Roh
Yong-Hee Kim
Jae-Won Ka
Nam-Seob Baek
Min-Kook Nah
Jae-Buem Oh
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Hwan-Kyu Kim
Soo-Gyun Roh
Yong-Hee Kim
Jae-Won Ka
Nam-Seob Baek
Min-Kook Nah
Jae-Buem Oh
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Priority claimed from KR1020030102338A external-priority patent/KR100575346B1/en
Priority claimed from KR1020030102339A external-priority patent/KR100575348B1/en
Application filed by Hwan-Kyu Kim, Soo-Gyun Roh, Yong-Hee Kim, Jae-Won Ka, Nam-Seob Baek, Min-Kook Nah, Jae-Buem Oh filed Critical Hwan-Kyu Kim
Publication of WO2004092185A1 publication Critical patent/WO2004092185A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic System without C-Metal linkages

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  • the present invention relates to new organic luminescent complex compounds containing rare earth metal ions and having a structure represented by a general formula shown below, as well as methods for preparing them.
  • the inventive complex compounds have an increased solubility in polymer medium through the design of their molecular structure so that they are effectively doped in the polymer medium.
  • the inventive compounds are used as planar waveguide-type optical amplifier materials that are new organic luminescent materials, of which photophysical properties are max-imized by the processes of absorbing and transferring artificial light using the principle of naturally occurring photosynthetic antenna complexes which show a light- harvesting effect by absorbing photon energy (or light) and transferring the absorbed energy to the central system of the complexes.
  • the inventive compounds have a structure where the rare earth metal ions are efficiently encapsulated with organic ligand derivatives.
  • the present invention relates to new planar waveguide-type optical amplifier materials having improved solubility and energy transfer capacity. Such materials compensate for light intensity reduction that is a fundamental problem with polymer materials for optical information processing.
  • the doping concentration of Er +3 in the existing silica optical fiber is about 100-1,000 ppm. If the doping concentration exceeds this limit, a non-light-emitting process will occur due to the interaction between the Er +3 ions, to cause a rapid reduction in optical amplification efficiency. For this reason, by the method of doping the silica optical fiber with Er +3 , it is impossible to perform high-gain optical amplification, and thus, it is difficult to achieve an optical amplification of about 30 dB in the form of planar waveguide-type optical integrated circuits. As new materials to solve this problem and to embody planar waveguide-type optical amplifier devices, polymer materials doped with rare earth metal ions are being noticed. Currently, in industrially advanced nations including Japan, USA and Europe, researches on the development of a planar waveguide-type optical amplifier material comprising a polymer medium doped with a complex compound containing rare earth ions are being conducted.
  • An optical fiber amplifier device prepared by doping a medium for a PMMA-based polymer optical fiber' s core with an organic dye at a doping concentration of about 1 ppm was first reported by Japan Keio University in 1993.
  • This optical device had a relatively large length of 50 cm and showed a very excellent optical amplification property of about 30 dB.
  • its optical amplification time is short due to its light- emitting process caused by spontaneous light emission, so that it cannot be used as the planar waveguide-type optical amplifier device.
  • this research team reported a polymer device for optical amplification prepared by doping a PMMA-based polymer optical fiber • with a rare earth metal having an amplification effect.
  • optical amplifier systems have a problem in that their optical amplification effect is insufficient since the doping concentration of the rare earth metals is limited due to the low solubility of the rare earth metals, and the phase separation between the rare earth ions and the silica occurs.
  • the present invention has been made to solve the above- mentioned problems occurring in the prior art, and an object of the present invention is to provide rare earth ion-containing organic ligand complex compounds having a structure represented by a general formula shown below, which are prepared by molecular engineering unlike the prior method of doping a polymer with rare earth ions, show a light-harvesting effect as the principle of natural photosynthesis, have excellent solubility in a polymer medium and have no aggregation and interaction between the rare earth metal ions.
  • Another object of the present invention is to provide methods for preparing dentritic porphyrin organic ligand complex compounds containing rare earth ions and having a structure represented by a general formula shown below.
  • Still another object of the present invention is to provide compounds showing an optical amplification effect and having a structure represented by a general formula shown below.
  • Still another object of the present invention is to provide organic ligand complex compounds whose photophysical properties can be controlled by a variety of rare earth metals such that they emit light at various wavelengths as shown in FIG. 6, as . well as methods for preparing them.
  • Still another object of the present invention is to provide a blend of a compound having a general formula shown below and a binder, the blend having an optical amplification effect • controlling photophysical properties.
  • the present invention provides complex compounds containing rare earth metal ions and having a structure represented by the following general formula, as well as methods for preparing them: [General Formula] wherein Ln is Yb, Er or Nd; a is 0, 1 or 2; B is
  • R a is H or F.
  • FIG. 1 shows the comparison of photoluminescence intensity between metal complexes
  • FIG. 2 shows the photoluminescence intensity of a complex compound substituted with dendron
  • FIG. 3 shows the effect of dendron in naphthalene
  • FIG. 4 shows the photoluminescence effect of naphthalene- dendron
  • FIG. 5 shows the comparison between Yb 3+ -(Pt-por 1) (terpy) and Yb 3+ - (G2-Pt-por 1) 3 (terpy);
  • FIG. 6 shows changes in photoluminescence wavelength and photoluminescence intensity with rare earth metals.
  • T. Baker Co. THF, ' hexane, toluene, chlorobenzene, dichloromethane, ethanol, acetone, HCl, KOH, and MgS0 4 which are commercially available from Sam Jun Chemical Co.
  • THF, hexane and toluene were used immediately after purification in the presence of Na/benzophenone, and CHC1 3 and CH 2 C1 2 were used immediately after purification in the presence of CaH 2 and P 2 0 5 .
  • the other substances were used without separate purification.
  • the structure of compounds prepared in the examples was analyzed by X H-NMR, 13 C-NMR and FT-IR spectrometric methods.
  • the title compound was prepared in the same manner as in Example ' 6 except that [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] platinum was used instead of 5, 10, 15-triphenyl-20- (4-methoxycarbonylphenyl) porphyrin.
  • Synthetic Example 17 Preparation of ([G-4]-5-(4- hydroxyphenyl) dipyrromethane) (Reaction Scheme 11) The title compound was prepared in the same manner as in Synthetic Example 14 except that [G-4]-Br was used instead of [G-1]-Br.
  • the title compound was prepared in the same manner as in Synthetic Example 4, using [G-l] 3 -5, 10, 15-triphenyl-20- (4- methoxy-carbonylphenyl) porphyrin .
  • Synthetic Example 26 Preparation of ( [G-l] 3 - [5, 10, 15- triphenyl-20- (4-methoxycarbonylphenyl) porphyrin] platinum) (Reaction Scheme 14)
  • the title compound was prepared in the same manner as in Synthetic Example 5, using [G-l] 3 -5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin.
  • Synthetic Example 36 Preparation of ( [G-3] 3- [5, 10, 15- triphenyl-20- (4-carboxyphenyl) porphyrin] zinc) (Reaction Scheme 16) The title compound was prepared in the same as in Synthetic Example 6, using [G-3] 3 - [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] zinc.
  • the title compound was prepared in the same as in Synthetic Example 6, using [G-4] 3 - [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] zinc.
  • Synthetic Example 44 Preparation of 9- (4-carbonylphenyl) - 10- (4-methoxyphenyl) anthracene (Reaction Scheme 20) The title compound was prepared in the same manner as in Synthetic Example 42 except that 1- (4-methylphenyl) -4- (4- methoxyphenyl) anthracene [AN-1] was used instead of l-(4- methylphenyl) -naphthalene [NA-1] .
  • FT-IR (KBr, c ⁇ rf ) 3300-2200 (very broad), 2925, 1683, 1600,
  • Synthetic Example 58 Preparation of [G-4] - [NA-3] 2 -C0 2 H (Reaction Scheme 34) The title compound was prepared in the same manner as in Synthetic Example 45 except that [G-4] - [NA-3] 2 -C0 2 Me was used instead of [NA-3] 2 -C0 2 Me.
  • Example 2 Preparation of Yb 3+ - (C 6 F 5 COO " ) 3 (Reaction Scheme 39) The title compound was prepared in the same manner as in Example 1 except that pentafluorobenzoic acid was used instead of benzonic acid. Also, Er 3+ - (C 6 F 5 COO " ) 3 and Nd 3+ - (C 6 F 5 COO " ) 3 were prepared in the same manner.
  • FT-IR (KBr, cm -1 ) : 1617, 1409.
  • Ra H or F
  • Ra H or F
  • the title compound was prepared in the same manner as in Example 5 except that bipyridine was used instead of terpyridine. Also, Er 3+ -([NA-1]-C0 2 " ) 3 (bipyridine) and Nd 3+ - ( [NA-1] -C0 2 " ⁇ ) 3 (bipyridine) were prepared in the same manner.
  • the title compound was prepared in the same manner as in Example 5 except that bipyridine was used instead of terpyridine. Also, Er 3+ - ( [NA-2] -C0 2 " ) 3 (bipyridine) and Nd 3+ - - ( [NA-2] -C0 2 " ) 3 (bipyridine) were prepared in the same manner.
  • the title compound was prepared in the same manner as in Example 5 except that [AN-1]-C0 2 H was used instead of [NA-1]-C0 2 H, and terpyridine was used instead of bipyridin. Also, Er 3+ - ( [AN- 1]-C0 2 ⁇ ) 3 (bipyridine) and Nd 3+ - ( [AN-1] -C0 2 ⁇ ) 3 (bipyridine) were prepared in the same manner.
  • the title compound was prepared in the same manner as in Example 5 except that [G-l] - [NA-2] -C0 2 H was used instead of [NA- 1]-C0 2 H. Also, Er 3+ -( [G-l] -[NA-2] -C0 2 " ) 3 (terpyridine) and Nd 3+ - ( [G-l] - [NA-2] -CO 2 " ) 3 (terpyridine) are prepared in the same manner.
  • the title compound was prepared in the same manner as in Example 5 except that [G-2] - [NA-2] -C0 2 H was used instead of [NA-' 1]-C0 2 H. Also, Er 3+ -([G-2]-[NA-2]-C0 2 " ) 3 (terpyridine) and Nd 3+ - ( [G-2] - [NA-2] -C0 2 ⁇ ) 3 (terpyridine) were prepared in the same manner.
  • Example 17 Preparation of Yb .3 J + ⁇ - ( [G-3] - [NA-2] -C0 2 " ) 3 (terpyridine) (Reaction Scheme 53)
  • the title compound was prepared in the same manner as in Example 5 except that [G-3] - [NA-2] -C0 2 H was used instead of [NA- 1]-C0 2 H.
  • Er 3+ -( [G-3] -[NA-2] -C0 2 ⁇ ) 3 (terpyridine) and Nd 3+ - ( [G-3] - [NA-2] -C0 2 " ) 3 (terpyridine) were prepared in the same manner.
  • the title compound was prepared in the same manner as in Example 5 except that [G-l] - [NA-3] 2 -C0 2 H was used instead of [NA- 1]-C0 2 H. Also, Er 3+ -( [G-l] - [NA-3] 2 -C0 2 " ) 3 (terpyridine) and Nd 3+ - ( [G-l] - [NA-3] 2 -C0 2 " ) 3 (terpyridine) were prepared in the same manner.
  • the title compound was prepared in the same manner as in Example 5 except that [G-2] - [NA-3] 2 -C0 2 H was used instead of [NA-1]-C0 2 H. Also, Er 3+ - ( [G-2] - [NA-3] 2 -C0 2 " ) 3 ' (terpyridine) and Nd 3+ -( [G-2] - [NA-3] 2 -C0 2 ⁇ ) 3 (terpyridine) were prepared in the same manner.
  • the title compound was prepared in the same manner as in Example 5 except that [G-3] - [NA-3] 2 -C0H was used instead of [NA-1]-C0 2 H. Also, Er 3+ - ( [G-3] - [NA-3] 2 -C0 2 " ) 3 (terpyridine) and Nd 3+ - ( [G-3 ] - [NA-3 ] 2 -C0 2 ) 3 (terpyridine) were prepared in the same manner .
  • the title compound was prepared in the same manner as in Example 5 except that [G-l] - [AN-1] -C0 2 H was used instead of [NA-1]-C0 2 H. Also, Er 3+ - ( [G-l] - [AN-1] -C0 2 " ) 3 (terpyridine) and Nd 3+ - ( [G-l] - [AN-1] -C0 2 " ) 3 (terpyridine) were prepared in 10. the same manner.
  • the title compound was prepared in the same manner as in Example 5 except that [G-3] - [AN-1] -C0 2 H was used instead of [NA- 1 ] -C0 2 H . Also, Er 3+ - ( [G-3 ] - [AN-1] -C0 2 " ) 3 (terpyridine) and Nd 3+ - ( [G-3 ] - [AN-1] -CO 2 " ) 3 (terpyridine ) were prepared in the same manner .
  • the title compound was prepared in the same manner as in Example 5 except that [G-4] - [AN-1] -C0 2 H was used instead of [NA-1]-C0 2 H. Also, Er 3+ - ( [G-4] - [AN-1] -C0 2 " ) 3 (terpyridine) and Nd 3+ - ( [G-4] - [AN-1] -C0 2 ⁇ ) 3 (terpyridine) were prepared in the same manner.
  • the title compound was prepared in the same manner as in Example 5 except that [G-l] - [AN-2] 2 -C0 2 H was used instead of [NA- 1]-C0 2 H. Also, Er 3+ -([G-l]-[AN-2] 2 -C0 2 " ) 3 (terpyridine) and Nd 3+ - ( [G-l] -[AN-2] 2-C02-) 3 (terpyridine) were prepared in the same manner.
  • the title compound was prepared in the same manner as in Example 5 except that [G-3] - [AN-2] 2 -C0 2 H was used instead of [NA- 1]-C0 2 H. Also, Er 3+ -( [G-3] - [AN-2] 2 -C0 2 " ) 3 (terpyridine) and Nd 3+ - ( [G-3] - [AN-2] 2 -C0 2 " ) 3 (terpyridine) were prepared in the same manner.
  • the title compound was prepared in the same manner as in Example 5 except that [G-4] - [AN-2] 2 -C0 2 H was used instead of [NA- 1]-C0 2 H. Also, Er 3+ -( [G-4] -[AN-2] 2 -C0 2 ⁇ ) 3 (terpyridine) and Nd 3+ - ( [G-4]- [AN-2] 2 -C0 2 ⁇ ) 3 (terpyridine) were prepared in the same manner.
  • Example 31 Preparation of Yb 3+ - [porphyrin (phenyl) 3 (COO )] 3 (Reaction Scheme 67) The title compound was prepared in the same manner as in Example 1, using 5, 10, 15-triphenyl-20- (4-carboxyphenyl) porphyrin. Also, Er 3+ - [porphyrin (phenyl) 3 (COO " ) ] 3 and Nd 3+ -
  • Example 1 except that [5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum was used instead of 5,10,15- triphenyl-20- (4-carboxyphenyl) porphyrin. Also, Er 3+ -
  • the title compound was prepared in the same manner as in Example 3, using 5, 10, 15-triphenyl-20- (4-carboxyphenyl) porphyrin, with the addition of anhydrous YbCl 3 and bipyridine. Also, Er 3+ - [porphyrin (phenyl) 3 (COO " ) ] 3 (bipyridine) and Nd 3+ -
  • M Zn or Pt
  • the title compound was prepared in the same manner as in Example 3 except that terpyridine was used instead of bipyridine.
  • Example 3 except that ( [5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum) was used instead of [5,10,15- triphenyl-20- (4-carboxyphenyl) porphyrin. • Also, Er 3+ - [porphyrin (phenyl) 3 (COO " ) platinum] 3 (terpyridine) and Nd 3+ -
  • M Zn or Pt
  • Example 1 using [G-2] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin. Also, Er 3+ - [ [G-2] 3 - porphyrin (phenyl) 3 (COO " ) ] 3 and Nd 3+ - [ [G-2] 3 -porphyrin (phenyl) 3 (COO " )] 3 were prepared in the same manner.
  • Example 1 using [G-3] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin. Also, Er 3+ - [ [G-3] 3 - porphyrin (phenyl) 3 (COO " ) ] 3 and Nd 3+ - [ [G-3] 3 -porphyrin (phenyl) 3 (COO "
  • the title compound was prepared in the same manner as in Example 1, using [ [G-l] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zince. Also, porphyrin (phenyl) 3 (COO " ) zinc] 3 and Nd 3- 3 + " * " - [ [G-l] 3 - porphyrin (phenyl) 3 (COO ⁇ ) zinc] 3 were prepared in the same manner.
  • the title compound was prepared in the same manner as in Example- 1, using [ [G-2] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er 3+ - [ [G-2] 3 - porphyrin (phenyl) 3 (COO " ) zinc] 3 and Nd 3+ - [ [G-2] 3 - porphyrin (phenyl) 3 (COO ⁇ ) zinc] 3 were prepared in the same manner.
  • Example 1 using [ [G-3] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er 3+ - [ [G-3] 3 - porphyrin (phenyl) 3 (COO " ) zinc] 3 and Nd 3+ - [ [G-3] 3 - porphyrin (phenyl) 3 (C00 ⁇ ) zinc] 3 were prepared in the same manner.
  • Example 47j Preparation of Yb 3+ - [ [G-4] 3 - porphyrin (phenyl) 3 (COO " ) zinc] 3 (Reaction Scheme 74)
  • the title compound was prepared in the same manner as in Example 1, using [ [G-4] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc.
  • Er 3+ - [ [G-4] 3 - porphyrin (phenyl) 3 (C00 ⁇ ) zinc] 3 and Nd 3+ - [ [G-4] 3 - porphyrin (phenyl) 3 (COO " ) zinc] 3 were prepared in the same amnner.
  • Example 48j Preparation of Yb 3+ - [ [G-l] 3 - porphyrin (phenyl) 3 (C00 ⁇ ) platinum] 3 (Reaction Scheme 74)
  • the title compound was prepared in the same manner as in Example 1, using [ [G-l] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] latinum.
  • Er 3+ - [ [G-l] 3 - porphyrin (phenyl) 3 (COO " ) platinum] 3 and Nd 3+ - [ [G-l] 3 - porphyrin (phenyl) 3 (COO " ) platinum] 3 were prepared in the same manner.
  • Example 49j Preparation of Yb 3+ - [ [G-2] 3 - porphyrin (phenyl) 3 (COO " ) platinum] 3 (Reaction Scheme 74)
  • the title compound was prepared in the same manner as in Example 1, using [ [G-2] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum.
  • Er 3+ - [ [G-2] 3 - porphyrin (phenyl) 3 (COO ⁇ ) platinum] 3 and Nd 3+ - [ [G-2] 3 - porphyrin (phenyl) 3 (COO ⁇ ) platinum] 3 were prepared in the same manner .
  • the title compound was prepared in the same manner as in Example 1, using [ [G-4] 3 -5, 10, 15-tri ⁇ henyl-20- (4- ca'rboxyphenyl) porphyrin] platinum. Also, Er 3+ - [ [G-4] 3 - porphyrin (phenyl) 3 (COO ) platinum] 3 and porphyrin (phenyl) 3 (COO " ) platinum] 3 were prepared in the same manner
  • the title compound was prepared in the same manner as in Example 3, using [G-2] 3 -5, 10, 15-Triphenyl-20- (4- carboxyphenyl) porphyrin with the addition of anhydrous YbCl 3 and bipyridine. Also, Er 3+ - [ [G-2] 3 -porphyrin (phenyl) 3 (COO ⁇ )] 3 (bipyridine) and Nd 3+ - [ [G-2] 3 -porphyrin (phenyl) 3 (COO " )] 3 (bipyridine) were prepared in the same manner.
  • Example 3 using [G-3] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin with the addition of anhydrous YbCl 3 and bipyridine.- Also, Er 3+ - [ [G-3] 3-porphyrin (phenyl) 3 (COO " ) ] 3 (bipyridine) and Nd 3+ - [ [G-3] 3-porphyrin (phenyl) 3 (COO "
  • the title compound was prepared in the same manner as in Example 3, using [ [G-2] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er 3+ - [ [G-2] 3 - porphyrin (phenyl) 3 (COO " ) zinc] 3 (bipyridine) and Nd 3+ - [ [G-2] 3 - porphyrin (phenyl) 3 (COO ⁇ ) zinc] 3 (bipyridine) were synthesized in the same manner.
  • the title compound was prepared in the same manner as Example 3, using [ [G-3] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl)porphypin] zinc. Also, Er 3+ - [ [G-3] 3 - porphyrin (phenyl) 3 (COO " ) zinc] 3 (bipyridine) and Nd 3+ - [ [G-3] 3 - porphyrin (phenyl) 3 (COO " ) zinc] 3 (bipyridine) were synthesized in the same manner.
  • the title compound was prepared in the same manner as in Example 3, using [ [G-l] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum. Also, Er 3+ - [ [G-l] 3 - porphyrin ( phenyl) 3 (COO ) platinum] 3 (bipyridine) and Nd 3+ - [ [G-l] 3 - porphyrin (phenyl) 3 (COO " ) platinum] 3 (bipyridine) were prepared in the same manner.
  • Example 62 Preparation of Yb 3+ - [ [G-3] 3 - porphyrin (phenyl) 3 (COO " ) platinum] 3 (bipyridine) (Reaction Scheme 76)
  • the title compound was prepared in the same manner as in Example 3, using [ [G-3] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum. Also, in the same manner,
  • Example 3 using [ [G-4] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum. Also, Er 3+ - [ [G-4] 3 - porphyrin (phenyl) 3 (COO " ) platinum] 3 (bipyridine) and Nd 3+ - [ [G-4] 3 - porphyrin (phenyl) 3 (COO ⁇ ) platinum] 3 (bipyridine) were synthesized in the same manner.
  • the title compound was prepared in the same manner as in Example 3 except that terpyridine was used instead of bipyridine. Also, Er 3+ - [ [G-l] 3 -porphyrin (phenyl) 3 (COO " ) ] 3 (terpyridine) and Nd 3+ - [ [G-l] 3 -porphyrin (phenyl) 3 (C00 ⁇ ) ] 3 (terpyridine) were prepared in the same manner.
  • Nd -[ [G-2] 3 -porphyrin (phenyl) 3 (COO ) ] 3 (terpyridine) were synthesized in the same manner .
  • Example 3 except that terpyridine was used bipyridine. Also, Er 3+ -[ [G-3] 3-porphyrin (phenyl) 3 (COO " ) ] 3 (terpyridine) and Nd 3+ -[[G-
  • Example 3 except that terpyridine was used instead of bipyridine.
  • the title compound was prepared in the same manner as in Example 3, using [ [G-l] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er 3+ - [ [G-l] 3 - porphyrin (phenyl) 3 (COO " ) zinc] 3 (terpyridine) ⁇ and Nd 3+ - [ [G-l] 3 - porphyrin (phenyl) 3 (COO " ) zinc] 3 (terpyridine) were prepared in the same manner.
  • Example 3 using [ [G-2 ] 3 -5 , 10 , 15-triphenyl-20- ( 4- carboxyphenyl)porphtrin] zinc. Also, Er 3+ - [ [G-2] 3 - porphyrin (phenyl) 3 (COO " ) zinc] 3 (terpyridine) and Nd 3+ - [ [G-2] 3 - porphyrin (phenyl) 3 (COO " ) zinc] 3 (terpyridine) were prepared in the same manner.
  • the title compound was prepared in the same manner as in Example 3, using [ [G-3] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er 3+ - [ [G-3] 3 - porphyrin (phenyl) 3 (COO ⁇ ) zinc] 3 (terpyridine) and Nd 3+ - [ [G-3] 3 - porphyrin (phenyl) 3 (COO ⁇ ) zinc] 3 (terpyridine) were prepared in the same manner.
  • the title compound was prepared in the same manner as in Example 3, using [ [G-4] 3 ⁇ 5, 10, 15 ⁇ triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er 3+ - [ [G-4] 3- porphyrin (phenyl ) 3 (COO " ) zinc] 3 (terpyridine ) and Nd 3+ - [ [G-4 ] 3 - porphyrin (phenyl ) 3 (COO " ) zinc] 3 (terpyridine ) were prepared in the same manner .
  • N Idd 33++ -- [[ [[GG--44 ]] 3 3--ppoorrpphhyyrriinn ((pphheennyyll )) 33 ((CCOOOO " ) zinc] 3 (terpyridine) : ⁇ e 190 , 1052 , 1323 nm ( ⁇ ex 442 nm, solid state )
  • Example 73 Preparation of Yb 3+ - [ [G-2] 3 - porphyrin (phenyl) 3 (C00 ⁇ ) platinum] 3 (terpyridine) (Reaction Scheme 78)
  • the -title compound was prepared in the same manner as in Example 3, using [ [G-2] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum.
  • Er 3+ - [ [G-2] 3 - porphyrin (phenyl ) 3 (COO " ) platinum] 3 (terpyridine ) and Nd 3+ - [ [G-2 ] 3 - porphyrin (phenyl) 3 (COO " ) platinum] 3 (terpyridine) were prepared in the same manner.
  • Example 74 Preparation of Yb 3+ - [ [G-3] 3 - porphyrin (phenyl) 3 (COO " ) platinum] 3 (terpyridine) (Reaction Scheme 78)
  • the title compound was prepared in the same manner as in Example 3, sing [ [G-3] 3 -5, 10, 15-triphenyl-20- (4- ' carboxyphenyl) porphyrin] latinum.
  • Er 3+ - [ [G-3] 3 - porphyrin (phenyl) 3 (COO " ) platinum] 3 (terpyridine) and Nd 3+ - [ [G-3] 3 - porphyrin (phenyl) 3 (C00 ⁇ ) platinum] 3 (terpyridine) were prepared in the same manner .
  • Example 75_ Preparation of Yb 3+ - [ [G-4] 3 - porphyrin (phenyl) 3 ( COO " ) platinum] 3 (terpyridine) (Reaction Scheme 78)
  • the title compound was prepared in the same manner as in Example 3, ' using [ [G-4] 3 -5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum.
  • Er 3+ - [ [G-4] 3 - porphyrin ( phenyl) 3 (COO " ) platinum] 3 (terpyridine) and Nd 3+ - [ [G-4] 3 - porphyrin (phenyl) 3 (COO " ) platinum] 3 (terpyridine) were prepared in the same manner.
  • Example 76 Photoluminescent properties of rare earth complex compounds
  • the formed thin film was irradiated with a 325-nm wavelength laser beam from a helium-cadmium (He-Cd) laser and measured for the photoluminescence intensities at the following wavelengths : ( 1 ) the photoluminescence intensity at a 978-nm wavelength, which corresponds to an electronic transition of 4 F 3/2 -> I11/2 that is the photoluminescent property of ytterbium (Yb ) ions ; ( 2 ) the photoluminescence intensity at a 1530-nm wavelength, which corresponds to an electronic transition of Ii3/ 2 -> I15 / 2 that is the photoluminescent property of erbium (Er) ions ; and ( 3 ) the photoluminescence intensity at a 1052-nm wavelength, which corresponds to an electronic transition of 2 F 5/2 -> F 7 / 2 that is the photoluminescent property of Nd ions .
  • He-Cd helium-cadmium
  • the photoluminescence intensity was increased with an increase in the content of the. complex compound, and when the content of the erbium complex was increased to 15% , the photoluminescence intensity at peak photoluminescence wavelength of erbium ions was 40 times increased .
  • the polymer thin film doped with the erbium complexes exhibited at least 30 times higher photoluminescence intensity than that of the silica optical fiber doped with rare earth ions , and thus had high optical amplification effect . Also, it could be found that this effect was shown also in the case of the ytterbium and Nd complexes .
  • the formed thin film was irradiated with a 442-nm wavelength laser beam from a helium-cadmium (He-Cd) laser and measured for the photoluminescence intensities at the following wavelengths: (1) the photoluminescence intensity at a 978-nm wavelength, which corresponds to an electronic transition of F3 /2 -> In /2 that is the photoluminescent property of ytterbium (Yb) ions; (2) the photoluminescence intensity at a 1530-nm wavelength, which corresponds to an electronic transition of 4 Ii3 / -> Ii 5/2 that is the photoluminescent property of erbium (Er) ions; and (3) the photoluminescence intensity at a 1052-nm wavelength, which corresponds to an electronic transition of 2 F 5/2 -> 4 F /2 that is the photoluminescent property of Nd ions.
  • He-Cd helium-cadmium
  • the photoluminescence intensity was increased with an increase in the content of the complex compound, and when the content of the erbium complex was increased to 15%, the photoluminescence intensity at peak photoluminescence wavelength of erbium ions was 125 times increased. Also, it could be found that the polymer thin film doped with the erbium complex exhibited at least 30 times higher photoluminescence intensity than that of the silica optical fiber doped with rare earth ions, and thus had high optical amplification effect. Also, it could be found that this effect was shown also in the case of the ytterbium and Nd complexes.
  • the rare earth ion- containing porphyrin complexes of the present invention have an excellent light-harvesting effect and an excellent solubility in polymer medium and do not show the aggregation phenomenon and thus interaction between the rare earth metal ions.
  • the complexes of the present invention have a very excellent optical amplification effect.
  • the present invention makes it possible to prepare the rare earth ion- organic ligand complexes whose photophysical properties can be controlled such that light can be • amplified at various wavelengths as shown in FIG. 6. Particularly, as apparent from Example 77 and FIGS. 2 to 5, the dendritic complexes have very high photoluminescence intensities at the respective wavelengths. This indicates that the compounds of the present invention have very excellent optical amplification properties.
  • the doping concentration of Er 3+ was limited to about 100-1,000 ppm.
  • concentration exceeds this limit, a non-light-emitting process will generally occur to cause a rapid reduction in optical amplification efficiency. For this reason, it is impossible to perform high-gain optical amplification, and thus, it is difficult to achieve an optical amplification of about 30 dB in the form of planar waveguide- type optical integrated circuits.
  • optical amplifier materials comprising an inorganic or organic polymer medium doped with rare earth ions, such as Er 3+ , or chelate complexes, have been conducted up to now.
  • rare earth ions such as Er 3+ , or chelate complexes
  • an effect of high optical amplification cannot be achieved since the doping concentration of the rare earth metals is limited due to the low solubility of the rare earth metals in the polymer medium.
  • the rare earth metals are used at high doping concentration, the aggregation between the metal ions and also the phase separation between the rare earth ions and the silica medium will occur to cause a reduction in optical amplification effect.
  • the present invention makes it possible to solve such problems occurring in the prior art. Namely, the present invention provides the rare earth ion-containing porphyrin complex compounds, which have a light-harvesting effect as shown in FIG. 1, and do not show the aggregation between the rare earth metals and thus the interaction between the rare earth metal ions. Also, as shown in FIG. 5, the dendritic complexes of the present invention have several times higher optical amplification effect than that of the prior material doped with the rare earth ions.
  • the present invention makes it possible to prepare the rare earth metal-containing organic ligand complex compounds whose photophysical properties can be controlled by suitable selection of the rare earth metal such that light at various wavelengths can be amplified as shown in FIG. 6.

Abstract

The present invention relates to new organic luminescent complex compounds containing rare earth metal ions, and methods for preparing the same. The compounds have photophysical properties which are maximized by processes of absorbing and transferring artificial light using the principle of photosynthetic antenna complexes. The compounds have a structure where the rare earth metal ions are efficiently encapsulated with organic ligand derivatives.

Description

LUMINESCENT LANTHANIDE (III) -CHELATED DENDRITIC COMPLEXES HAVING LIGHT-HARVESTING EFFECT AND THEIR SYNTHETIC METHODS
Technical Field
The present invention relates to new organic luminescent complex compounds containing rare earth metal ions and having a structure represented by a general formula shown below, as well as methods for preparing them. The inventive complex compounds have an increased solubility in polymer medium through the design of their molecular structure so that they are effectively doped in the polymer medium. Also, the inventive compounds are used as planar waveguide-type optical amplifier materials that are new organic luminescent materials, of which photophysical properties are max-imized by the processes of absorbing and transferring artificial light using the principle of naturally occurring photosynthetic antenna complexes which show a light- harvesting effect by absorbing photon energy (or light) and transferring the absorbed energy to the central system of the complexes. Moreover, the inventive compounds have a structure where the rare earth metal ions are efficiently encapsulated with organic ligand derivatives.
Background Art
The present invention relates to new planar waveguide-type optical amplifier materials having improved solubility and energy transfer capacity. Such materials compensate for light intensity reduction that is a fundamental problem with polymer materials for optical information processing.
The doping concentration of Er+3 in the existing silica optical fiber is about 100-1,000 ppm. If the doping concentration exceeds this limit, a non-light-emitting process will occur due to the interaction between the Er+3 ions, to cause a rapid reduction in optical amplification efficiency. For this reason, by the method of doping the silica optical fiber with Er+3, it is impossible to perform high-gain optical amplification, and thus, it is difficult to achieve an optical amplification of about 30 dB in the form of planar waveguide-type optical integrated circuits. As new materials to solve this problem and to embody planar waveguide-type optical amplifier devices, polymer materials doped with rare earth metal ions are being noticed. Currently, in industrially advanced nations including Japan, USA and Europe, researches on the development of a planar waveguide-type optical amplifier material comprising a polymer medium doped with a complex compound containing rare earth ions are being conducted.
An optical fiber amplifier device prepared by doping a medium for a PMMA-based polymer optical fiber' s core with an organic dye at a doping concentration of about 1 ppm was first reported by Japan Keio University in 1993. This optical device had a relatively large length of 50 cm and showed a very excellent optical amplification property of about 30 dB. However, its optical amplification time is short due to its light- emitting process caused by spontaneous light emission, so that it cannot be used as the planar waveguide-type optical amplifier device. In an attempt to overcome this problem, this research team reported a polymer device for optical amplification prepared by doping a PMMA-based polymer optical fiber • with a rare earth metal having an amplification effect. Recently, a Kuzyk' s research team in USA Texas-Austin University reported an optical amplifier device having a very short length of 2.2 cm, which had been prepared by doping photolime gel, a water-soluble polymer, with Nd+3, by a spin coating method. This optical amplifier device had an amplification wavelength of 1.06 μm and an amplification gain of 8.5 dB. Also, Dutch Philips Company developed a polymer optical fiber-type optical amplifier device having a very short length of about 1.5 cm, which had been prepared by filling a Teflon capillary tube with a lauryl methacrylate monomer (MA series) , doping the monomer with Eu+3, and then polymerizing the doped monomer. This amplifier device was reported to have an amplification gain of 4.1 dB.
Recently, in many research institutes, including a Japan's NTT's photonic research team, several USA universities (Colorado University and Arizona University) and research institutes (Bellcore and Corning) and Canada McGill University, researches on optical amplifier materials prepared by uniformly introducing rare earth metals into an inorganic polymer material (Si02) by low-temperature sol-gel chemistry are being actively conducted. Particularly, in 1996, the development of a planar waveguide- type optical amplifier device and an optical amplifier device integrated with WDM was reported. However, such optical amplifier systems have a problem in that their optical amplification effect is insufficient since the doping concentration of the rare earth metals is limited due to the low solubility of the rare earth metals, and the phase separation between the rare earth ions and the silica occurs.
Disclosure of Invention
The present invention has been made to solve the above- mentioned problems occurring in the prior art, and an object of the present invention is to provide rare earth ion-containing organic ligand complex compounds having a structure represented by a general formula shown below, which are prepared by molecular engineering unlike the prior method of doping a polymer with rare earth ions, show a light-harvesting effect as the principle of natural photosynthesis, have excellent solubility in a polymer medium and have no aggregation and interaction between the rare earth metal ions.
Another object of the present invention is to provide methods for preparing dentritic porphyrin organic ligand complex compounds containing rare earth ions and having a structure represented by a general formula shown below.
Still another object of the present invention is to provide compounds showing an optical amplification effect and having a structure represented by a general formula shown below.
Still another object of the present invention is to provide organic ligand complex compounds whose photophysical properties can be controlled by a variety of rare earth metals such that they emit light at various wavelengths as shown in FIG. 6, as . well as methods for preparing them.
Still another object of the present invention is to provide a blend of a compound having a general formula shown below and a binder, the blend having an optical amplification effect • controlling photophysical properties. To achieve the above objects, the present invention provides complex compounds containing rare earth metal ions and having a structure represented by the following general formula, as well as methods for preparing them: [General Formula]
Figure imgf000006_0001
wherein Ln is Yb, Er or Nd; a is 0, 1 or 2; B is
Figure imgf000006_0002
Figure imgf000006_0003
and Ra is H or F.
Concretely, the compounds of the general formula are represented by the following chemical formulas (1)-(17):
[Chemical Formula 1] [Chemical Formula 2]
Figure imgf000007_0001
where x= 1 or 2;
[Chemical Formula 4]
Figure imgf000007_0002
where x=l or 2; [Chemical Formula 5]
Figure imgf000007_0003
where x=l or 2; [Chemical Formula 6]
Figure imgf000008_0001
[Chemical Formula 7]
Figure imgf000008_0002
[Chemical Formula 8]
Figure imgf000009_0001
[Chemical Formula 9]
Figure imgf000009_0002
[Chemical Formula 10]
Figure imgf000010_0001
[Chemical Formula 13]
Figure imgf000011_0001
Chemical Formula 14]
Figure imgf000011_0002
[Chemical Formula 15]
Figure imgf000011_0003
[Chemical Formula 16]
Figure imgf000012_0001
[Chemical Formula 17 ]
Figure imgf000012_0002
Brief Description of Drav?ings
FIG. 1 shows the comparison of photoluminescence intensity between metal complexes;
FIG. 2 shows the photoluminescence intensity of a complex compound substituted with dendron;
FIG. 3 shows the effect of dendron in naphthalene;
FIG. 4 shows the photoluminescence effect of naphthalene- dendron;
FIG. 5 shows the comparison between Yb3+-(Pt-por 1) (terpy) and Yb3+- (G2-Pt-por 1)3 (terpy); and
FIG. 6 shows changes in photoluminescence wavelength and photoluminescence intensity with rare earth metals.
Best Mode for Carrying Out the Invention
' Hereinafter, the present invention will be described in detail by examples for the synthesis of intermediates and examples for the preparation of rare earth ion-containing luminescent complex compounds. However, it will be obvious to a person skilled in the art that the present invention is not limited to or by the examples.
In the examples, the following substances were used to prepare the compounds of the present invention: KH (dispersion in mineral oil) , pyrrole, benzaldehyde, 4-hydroxybenzaldehyde, trifluoroacetic acid (TFA) , BF3-OEt2, 2, 2' -dipyridyl, and 2, 2' : 6' , 2' ' -terphyridine, which are commercially available from Aldrich Co.; pentafluorobenzoic acid which is commercially available from TCI Co.; methyl-4-formylbenzoate which is commercially available from Fluka Co.; 2, 3-dichloro-5, 6-dicyano- 1, 4-benzoquinone (DDQ) which is commercially available from Acros Co.; benzoic acid which is commercially available from Janssen Co.; anhydrous ErCl3 which is commercially available from Stem Co.; anhydrous YbCl3 and anhydrous NdCl3 which are commercially available from Aldrich Co.; absolute ethanol and methanol which are commercially available from J. T. Baker Co.; and THF, ' hexane, toluene, chlorobenzene, dichloromethane, ethanol, acetone, HCl, KOH, and MgS04 which are commercially available from Sam Jun Chemical Co. Of such substances, THF, hexane and toluene were used immediately after purification in the presence of Na/benzophenone, and CHC13 and CH2C12 were used immediately after purification in the presence of CaH2 and P205. The other substances were used without separate purification. The structure of compounds prepared in the examples was analyzed by XH-NMR, 13 C-NMR and FT-IR spectrometric methods. The H-NMR results were recorded using a Varian 300 spectrometer, and all chemical shifts were recorded in ppm units per tetramethyl silane as the internal standard. IR spectra were measured on KBr pellets using a Perkin-Elmer spectrometer. Luminescent spectra were measured in a solid state by FS920 (Edinburgh Instruments Ltd.)
Hereinafter, examples for the synthesis of intermediates, examples for the preparation of complex compounds of the present invention, and examples for the preparation of a blend consisting of the compound prepared in the preparation examples and a- polymer substance, such as fluorinated or non-fluorinated polystyrene, polyimide, polymethylmethacrylate, polyamide, polyether or polyester, and the photoluminescence efficiency of the blend, will be described. However, it will be obvious to a person skilled in the art that the present invention is not limited by or to the examples.
Synthesis of Intermediates Synthetic' Example 1: Preparation of 5-Phenyldipyrromethane (Reaction Scheme 1)
31. 61 g (471.16 mmol) of pyrrole and 10 g (94.23 mmol) were introduced into a round-bottom flask, and stirred for 5 minutes at room temperature. The stirred material was added with 726 μl (9.42 mmol) of trifluoroacetic acid (TEA) and stirred for 5 minutes at room temperature, after which 25 ml of 0. IN NaOH aqueous solution was introduced into the reactor to terminate the reaction. After the reaction mixture was extracted with dichloromethane, the organic solvent and the pyrrole were completely evaporated. The remaining material was distilled in vacuum using a Kugelrohr apparatus to give a yellow compound. The yellow compound obtained by the distillation was dissolved in ethanol and recrytallized by the addition of a small amount of water to give a white crystal.
^Η NMR (CDCI3, ppm) : 5.47 (s, 1H, meso-H) , 5.91 (m, 2H, pyrrole- H) , 6.15 (q, 2H, pyrrole-H), 6.69 (q, 2H, pyrrole-H), 7.19-7.35 (m, 5H, Ar-H) , 7.89 (br s, 2H, NH) [Reaction Scheme 1]
Figure imgf000015_0001
Synthetic Example 2 Preparation of 5- (4- methoxycarbonylphenyl) dipyrromethane (Reaction Scheme2)
The title compound was prepared under the same conditions as in Synthetic Example 1 except that 4-methyl 4-formylbenzoate was used instead of benzaldehyde. E NMR (CDCI3, ppm) : 3.90 (s, 3H, CH3) , 5.47 (s, 1H, meso-
H) , 5.89 (m, 2H, pyrrole-H), 6.16 (q, 2H, pyrrole-H), 6.71 (q,
2H, pyrrole-H), 7.96 (m, 4H, Ar-H and NH) '
[Reaction Scheme 2 ]
Figure imgf000015_0002
Synthetic Example 3: Preparation of (5, 10, 15-triphenyl-20- (4-methoxy-carbonylphenyl) porphyrin) (Reaction Scheme3)
1.76g (7.92mmol) of phenyldipyrromethane, 2.22 g (7.92 mmol) of (5- (4-methoxy-carbonylphenyl) dipyrromethane, 1.68 g (1.84 mmol) of benzaldehyde and 792 mL (~10~2 M) of CHC13 were introduced into a reaction flask and stirred for 10 minutes at room temperature. The stirred mixture was added with 502 μL (3.96 mmol) of BF3-OEt2 and stirred for 30 minutes at room temperature, and then, added with 5.39 g (23.76 mmol) of DDQ and stirred for one hour. The resulting solution was distilled under reduced pressure to remove the solvent. The remaining material was separated by column chromatography (silica, CHC13) and then washed with cold ethanol to give the title compound.
2H NMR (CDC13, ppm) : δ 8.95-8.97 (d, 6H, β-pyrrole) , 8.88- 8.89 (d, 2H, β-pyrrole) 8-.52-8.55 (d, 2H, Ar-H), 8.39-8.42 (d, 2H, Ar-H), 8.31-8.33 (m, 6H, Ar-H), 7.83-7.84 (m, 9H, Ar-H), 4.11 (s, 3H , -OCH3), -2.68 (s, 2H, NH) [Reaction Scheme 3]
Figure imgf000016_0001
Synthetic Example 4 : . Preparation of ( [5, 10 , 15-Triphenyl-20- ( 4-methoxycarbonylphenyl) porphyrin] zinc (Reaction Scheme 4 )
0.88 (1.31 αimol) of 5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin, 1.'44 g (6.55 mmol) of zinc acetate dihydrate and 50 ml of THF 50 were introduced into a reaction flask and stirred < at reflux overnight. After completion of the reaction, the reaction mixture was cooled to room temperature, extracted with CHC13, and washed several times with aqueous sodium bicarbonate solution and water. The organic layer was dried with anhydrous sodium sulfate and the solvent was removed under reduced pressure. The remaining material was washed with cold ethanol, and dried under vacuum to give the title compound.
XH NMR (CDCI3, ppm) : δ 8.86 (s, 6H, β-pyrrole), 8.80 (d, 2H, β- pyrrole), 8.48 (d, 2H, Ar-H), 8.32 (d, 2H, Ar-H), 8.22 (d, 6H,
Ar-H), 7.77 (m, 9H, Ar-H), 4.11 (s, 3H, -OCH3) [Reaction Scheme 4]
Figure imgf000017_0001
Synthetic Example 5: Preparation of ( [5, 10, 15-Triphenyl-20- (4-methoxycarbonylphenyl)porphyrin]platinum) (Reaction Scheme 5)
0.311 g (0.462 mmol) of 5, 10, 15-tripheny-20- (4- methoxycarbonylphenyl) porphyrin, 0.246 g (0.924 mmol) of platinum (II) chloride and 25 ml of benzonitrile were introduced • into a reaction flask, and stirred at reflux for 30 hours. After completion of the reaction, the reaction mixture was cooled to room temperature. After the cooled material was diluted with CHC12, the solvent was completely removed under reduced pressure. The remaining material was separated by column chromatography (silica, MC) to give the title compound. λH NMR (CDCI3, ppm) : δ 8.76 (s, 6H, β-pyrrole), 8.69 (d, 2H, β- pyrrole), 8.50 (d, 2H, Ar-H), 8.30 (d, 2H, Ar-H), 8.27 (d, 6H, Ar-H), 7.75 (m, 9H, Ar-H), 4.11 (s, 3H, -OCH3) [Reaction Scheme 5]
Figure imgf000018_0001
Synthetic Example 6: Preparation of (5, 10, 15-Triphenyl-20- (4-carboxyphenyl) porphyrin) (Reaction Scheme 6) 0.94 g (1.39 mmol) of 5, 10, 15-triphenyl-20- (4- methoxycarbonyl) porphyrin, 0.78 g (13.97 mmol) of KOH, THF- ethanol (1:1), and distilled water were' introduced into a reaction flask and stirred at reflux overnight. After completion of the reaction, the reaction solution was cooled to room temperature and adjusted to a pH of 2 by the addition of concentrated hydrochloric acid. This was extracted with CHC13, and the organic layer was washed several times with aqueous sodium bicarbonate solution and water, and dried with anhydrous sodium sulfate. • The solvent was removed under reduced pressure, and the residue was separated by flash column chromatography (Silica; CHC13 : MeOH = 9 : 1) . The product was washed with cold ethanol and dried under vacuum to give the title compound. XH NMR (CDCI3, ppm) : δ 8.86 (s, 6H, β-pyrrole), 8.80 (d, 2H, β- pyrrole), 8.48 (d, 2H, Ar-H), 8.32 (d, 2H, Ar-H), 8.22 (d, 6H, Ar-H), 7.77 ( , 9H, Ar-H), -2.65 (s, 2H, NH) [Reaction Scheme 6]
Figure imgf000019_0001
Synthetic Example 7: Preparation of ( [5, 10, 15-triphenyl-20- (4-carboxyphenyl) porphyrin] zinc) (Reaction Scheme 7)
The title compound was prepared in the same manner as in Example 6 except that [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] zinc was used instead of 5,10, 15-triphenyl-20- (4- ethoxycarbonylphenyl) porphyrin. 1H NMR (CDCI3, ppm) : δ 8.86 (s, 6H, β-pyrrole), 8.80 (d, 2H, β- pyrrole) , 8.48 (d, 2H, Ar-H), 8.32 (d, 2H, Ar-H), 8.22 (d, 6H, Ar-H) , 7.77 (m, 9H, Ar-H) [Reaction Scheme 7]
Figure imgf000019_0002
Synthetic Example 8: Preparation of ( [5, 10, 15-triphenyl-20- (4-carboxyphenyl) porphyrin] platinum) (Reaction Scheme 8)
The title compound was prepared in the same manner as in Example ' 6 except that [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] platinum was used instead of 5, 10, 15-triphenyl-20- (4-methoxycarbonylphenyl) porphyrin.
XH NMR (CDC13, ppm) : δ 8.76 (s, 6H, β-pyrrole), 8.69 (d, 2H, β-pyrrole), 8.50 (d, 2H, Ar-H), 8.30 (d, 2H, Ar-H), 8.27 (d, 6H, Ar-H), 7.75 ( , 9H, Ar-H) [Reaction Scheme 8]
Figure imgf000020_0001
Synthetic Example Preparation of (5-(4- hydroxyphenyl) dipyrromethane (Reaction Scheme 9)
27.47 g (409.43 mmol) of pyrrole and 10 g (81.88 mmol) of 4-hydroxybenzaldehyde were introduced into a round-bottom flask and stirred for 5 minutes at room temperature. The solution was added with 630.85 μl (8.19 mmol) of trifluoroacetic acid (TFA) , and stirred for 5 minutes at room temperature. ' 25 ml of 0. IN NaOH aqueous solution was introduced into the reactor to terminate the reaction. After the resulting solution was extracted with dichloromethane, the organic solvent and the pyrrole were completely evaporated. - The remaining material was separated by column chromatography (silica; MC/EA=4:1) to give the title compound.
XH NMR (CDCI3, ppm) : 5.25 (s, 1H, meso-H) , 5.91 (s, 1H, OH), 6'.17 (m, 2H, pyrrole-H), 6.67 (m, 2H, pyrrole-H), 6.73 (d, 2H, Ar-H), 7.06 (d, 2H, Ar-H), 7.94 (br s, 2H, NH) ■ [Reaction Scheme 9]
Figure imgf000021_0001
Synthetic Example 10: Preparation of [G-l] -aldehyde (Reaction Scheme 10)
0.3 g (2.45 mmol) of 4-hydroxybenzaldehyde, 1.98 g (2.45 mmol) of [G-1]-Br, 1.70 g (12.28 mmol) of K2C03, 100 ml of acetone and a small amount of water were introduced into a reaction flask and stirred at reflux for 24 hours. After completion of the reaction, the solution was cooled to room temperature, and the solvent was removed under reduced pressure. The remaining material was extracted with MC and dried with anhydrous MgS04. After the solvent was removed under reduced pressure, the residue was separated by column chromatography (silica; MC) to give the title compound.
XH NMR (CDC13, ppm) : 5.04 (s, 4H) , 5.08 (s, 2H) , 6.52 (t, 1H) , 6.66 (d, 2H) , 7.04 (d, 2H) , 7.40-7.35 (m, 10H) , 7.82 (d, 2H) , 9.88 (s, 1H)
Synthetic Example 11: Preparation of [G-2] -aldehyde
(Reaction Scheme 10)
The title compound was prepared in the same manner as in
Synthetic Example 10 except that [G-2]-Br was used instead of
[G-1]-Br. XH NMR (CDCI3, ppm) : 4.92 (s, 4H) , 4.97 (ar, 8H) , 4.99 (s, 2H) ,
6.54 (t, 1H) , 6.62 (d, 2H) , 6.65 (d, 4H) , 7.04 (d, 2H) , 7.20-
7.38 (m, 20H) , 7.76 (d, 2H) , 9.79 (s, 1H) Synthetic Example 12: Preparation of [G-3] -aldehyde (Reaction Scheme 10)
The title compound was prepared in the same manner as in Synthetic Example 10 except that [G-3]-Br was used instead of [G-1]-Br.
*H NMR (CDC13, ppm) : 4.95 (s, 24H) , 4.98 (s, 4H) , 5.16 (s, 2H) , 6.52 (t, 4H) , 6.55 (t, 2H) , 6.62 (t, IH) , 6.65 (d, 8H) , 6.71 (d, 4H), 6.87 (d, 2H) , 7.21-7.38 (m, 42H) , 8.08 (d, 2H) , 9.80 (s, IH)
Synthetic Example 13: Preparation of [G-4] -aldehyde (Reaction Scheme 10)
The title compound was prepared in the same manner as in Synthetic Example 10 except that [G-4]-Br was used instead of [G-1]-Br.
XH NMR (CDCI3, ppm) : 4.75-4.69 (s, 56H) , 4.91 (s, 4H) , 5.06 (s, 2H) , 6.48 (t, 8H) , 6.'52 (t, 4H) , 6.55 (t, 2H) , 6.60. (t, IH) , 6.62 (d, 16H), 6.65 (d, 8H) , 6.71 (d, 4H) , 6.87 (d, 2H) , 7.21- 7.38 (m, 82H) , 7.98 (d, 2H) , 9.82 (s, IH) [Reaction Scheme 10]
-[Gn]
OH O'
K,C03
[Gn]-Br
Acetone /water
~. , reflux
CHO CHO
Figure imgf000023_0001
(G-l) (G-2)
Figure imgf000023_0002
(G-3) (G-4)
Synthetic Example 14: Preparation of [G-l] -5- (4- hydroxyphenyl) dipyrromethane (Reaction Scheme 11) The title compound was prepared in the same manner as in Synthetic Example 10 except that 5- (4- hydroxyphenyl) dipyrromethane was used instead of 4- hydroxybenzaldehyde . XH NMR (CDCI3, ppm) : 5.04 (s, 4H) , 5.08 (s, 2H) , 5.25 (s, IH, meso-H) , 6.17 (m, 2H, pyrrole-H), 6.52 (t, IH) , 6.66 (d, 2H) , 6.67 ( , 2H, pyrrole-H), 6.73 (d, 2H, Ar-H), 7.06 (d, 2H, Ar-H), 7.40-7.35 (m, 10H) , 7.94 (br s, 2H, NH)
Synthetic Example 15: Preparation of ( [G-2] -5- (4- hydroxyphenyl) dipyrromethane (Reaction Scheme 11)
The title compound was prepared in the same manner as in Synthetic Example 14 except that [G-2]-Br was used instead of [G-1]-Br.
XE NMR (CDCI3, ppm) : 4.92 (s, 4H) , 4.97 (s, 8H) , 4.99 (s, 2H) , 5.25 (s, IH, meso-H), 6.17 ( , 2H, pyrrole-H), 6.54 (t, IH) , 6.62 (d, 2H) , 6.65 (d, 2H) , 6.67 (m, 2H, pyrrole-H), 6.73 (d, 2H, Ar-H), 7.06 (d, 2H, Ar-H), 7.20-7.38 ( , 20H) , 7.94 (br s, 2H, NH)
Synthetic Example 16: Preparation of ([G-3]-5-(4- hydroxyphenyl) dipyrromethane) (Reaction Scheme 11)
The title compound was prepared in the same manner as in Synthetic Example 14 except that [G-3]-Br was used instead of [G-1]-Br.
XH NMR (CDCI3, ppm) : 4.95 (s, 24H) , 4.98 (s, 4H) , 5.16- (s, 2H) , 5.25 (s, IH, meso-H), 6.17 (m, 2H, pyrrole-H), 6.52 (t, 4H) , 6:55 (t, 2H) , 6.62 (t, IH) , 6.65 (d, 8Η) , 6.67 ( , 2H, pyrrole- H) , 6.71 (d, 4H) , 6.73 (d, 2H, Ar-H), 6.87 (d, 2H) , 7.06 (d, 2H, Ar-H), 7.20-7.38 (m, 42H) , 8.80 (d, 2H) , 7.94 (br s, 2H, NH)
Synthetic Example 17: Preparation of ([G-4]-5-(4- hydroxyphenyl) dipyrromethane) (Reaction Scheme 11) The title compound was prepared in the same manner as in Synthetic Example 14 except that [G-4]-Br was used instead of [G-1]-Br.
XH NMR (CDC13, ppm) : 4.75-4.69 (s, -56H) , 4.91 (s, 4H) , 5.06 (s, 2H) , 5.25 (s, IH, meso-H),' 6.17 ( , 2H, pyrrole-H), 6.48 (t, 8H) , 6.52 (t, 4H) , 6.55 (t, 2H) , 6.60 (t, IH) , 6.62 (d, 16H) , 6.65 (d, 8H) , 6.67 (m, 2H, pyrrole-H), 6.71 (d, 4H) , 6.73 (d, 2H, Ar-H), 6.87 (d, 2H) , 7.06 (d, 2H, Ar-H), 7.21-7.38 (m, 82H) , 7.98 (d, 2H) , 7.94 (br s, 2H, NH)
[Reaction Scheme 11 ]
Figure imgf000025_0001
Synthetic Example 18: Preparation of ( [G-l] 3-5, 10, 15- triphenyl-20- (4-methoxy-carbonylphenyl) porphyrin) (Reaction
Scheme 12) •
The title compound was prepared in the same manner as in Synthetic Example 3, using [G-l] -5-phenyldipyrromethane, (5- (4- methoxy-carbonylphenyl) dipyrromethane, [G-l] -benzaldehyde . XH NMR (CDCI3, ppm) : δ -2.68 (s, 2H) , 4.11 (s, 3H) , 5.11 (s, 12H) , 5.23 (s, 6H) , 6.68 (t, 3H) , 6.87 (d, 6H) , 7.30-7.46. (m, 36H), 8.31 (m, 6H) , 8.39 (d, 2H) , 8.52 ' (d, 2H) , 8.95 (d, 6H) , 8.88 (d, 2H)
Synthetic Example 19: Preparation of ( [G-2]3-5, 10, 15- triphenyl-20- (4-methoxy-carbonylphenyl) porphyrin) (Reaction
Scheme 12) The title compound was prepared in the same manner as in Synthetic Example 3, using [G-2] -5-phenyldipyrromethane, (5- (4- methoxy-carbonylphenyl) dipyrromethane, [G-l] -benzaldehyde. ' XH NMR (CDCI3, ppm) : δ -2.69 (s, 2H) , 4.12 (s, 3H) , 5.03 (s, 24H), 5.05 (s, 12H) , 5.25 (s, 6H) , 6.58 (t, 6H) , 6 63 (t, 3H) , 6.73 (d, 12H) , 6.86 (d, 6H) , 7.23-7.40 (m, 66H) , 8.10 (m, 6H) , 8.39 (d, 2H) , 8.52 (d, 2H) , 8.95 (d, 6H) , 8.88 (d, 2H)
Synthetic Example 20: Preparation of ( [G-3J3-5, 10, 15- triphenyl-20- (4-methoxy-carbonylphenyl) porphyrin) (Reaction
Scheme 12)
The title compound was prepared in the same manner as in Synthetic Example 3, using [G-3] -5-phenyldipyrromethane, (5- (4- methoxy-carbonylphenyl) dipyrromethane, [G-3] -benzaldehyde. XH NMR (CDCI3, ppm) : δ -2.72 (s, 2H) , 4.12 (s, 3H) , 4.95 (s, 72H), 5.02 (s, 12H), 5.22 (s, 6H) , 6.52 ' (t, 12H) , 6.55 (t, 6H) , 6.62 (t, 3H), 6.65 (d, 24H) , 6.71 (d, 12H) , 6.87 (d, 6H) , 7.'21- 7.38 (m, 126H), 8.08 (m, 6H) , 8.39 (d, 2H) , 8.52 (d, 2H) , 8.95 (d, 6H) , 8.88 (d, 2H)
Synthetic Example 21: Preparation of ( [G-4]3-5, 10, 15- triphenyl-20- (4-methoxy-carbonylphenyl) porphyrin) (Reactoion
Scheme 12)
The title compound was prepared in the same manner as in Synthetic Example 3, using [G-4] -5-phenyldipyrromethane, (5- (4- methoxy-carbonylphenyl) dipyrromethane, [G-4] -benzaldehyde. 2H NMR (CDCI3, ppm) : δ -2.72 (s, 2H) , 4.12 (s, 3H) , 4.75-4.69 (s, 168H) , 4.91 (s, 12H) , 5.06 (s, 6H) , 6.48 (t, 24H) , 6.52 (t, 12H) , 6.55 (t, 6H), 6.62 (t, 3H) , 6.62 (d, 48H) , 6.65 (d, 24H) , 6.71 (d, 12H) , 6.87 (d, 6H) , 7.19-7.38 ( , 252H) , 8.08 (m, 6H) , 8.39 (d, 2H), 8.52 (d, 2H), 8.95 (d, .6H) , 8.88 (d, 2H) [Reaction Scheme 12]
Figure imgf000027_0001
Synthetic Example 22: Preparation of ( [G-l] 3- [5, 10, 15- Triphenyl-20- (4-methoxycarbonylphenyl) porphyrin] zinc) (Reaction Scheme 13)
The title compound was prepared in the same manner as in Synthetic Example 4, using [G-l] 3-5, 10, 15-triphenyl-20- (4- methoxy-carbonylphenyl) porphyrin .
1R NMR (CDC13, ppm) : δ 4.11 (s, 3H) , 5.11 (s, 12H) , 5.23 (s, 6H) , 6.68 (t, 3H) , 6.87 (d, 6H) , 7.30-7.46 (m, 36H) , 8.31 (m, 6H) , 8.39 (d, 2H),'8.52 (d, 2H), 8.95 (d, 6H) , 8.88 (d, 2H)
Synthetic Example 23: Preparation of ( [G-2] 3- [5, 10, 15-
Triphenyl-20- (4-methoxycarbonylphenyl) porphyrin] zinc) (Reaction
Scheme 13)
The title compound was prepared in the same manner as in
Synthetic Example 4, using [G-2] 3-5, 10, 15-triphenyl-20- (4- methoxy-carbonylphenyl) porphyrin. (Compounds which contain G-3 and G-4, respectively, were prepared in the same manner, using
G-3 and G-4) .
XH NMR (CDCI3, ppm) : δ 4.12 (s, 3H) , 5.03 (s, 24H) , 5.05 (s,
12H), 5.25 (s, 6H), 6.58 (t, 6H) , 6.63 (t, 3H) , 6.73 (d, 12H) , 6.86 (d, 6H) , 7.23-7.40 (m, 66H) , 8.10 (m, 6H) , 8.39 (d, 2H) ,
8.52 (-d, 2H) , 8.95 (d, 6H) , 8.88 (d, 2H) Synthetic Example 24: Preparation of ( [G-3] 3- [5, 10, 15- Triphenyl-20- ( -methoxycarbonylphenyl) porphyrin] zinc) (Reaction Scheme 13) The title compound was prepared in the same manner as in Synthetic Example 4, ■ using [G-3] 3-5, 10, 15-triphenyl-20- (4- methoxy-carbonylphenyl) porphyrin'.
XH NMR (CDC13, ppm) : δ 4.12 (s, 3H) , 4.95 (s, 72H) , 5.02 (s, 12H) , 5.22 (s, 6H) , 6.52 (t, 12H) , 6.55 (t, 6H) , 6.62 (t, 3H) , 6.65 (d, 24H) , 6.71 (d, 12H) , 6.87 (d, 6H) , 7.21-7.38 (m, 126H) , 8.08 ( , 6H), 8.39 (d,- -2H) , 8.52 (d, 2H) , 8.95 (d, 6H) , 8.88 (d, 2H)
Synthetic Example 25: Preparation of ( [G-4] 3- [5, 10, 15- triphenyl-20- (4-methoxycarbonylphenyl) porphyrin] zinc) (Reaction
Scheme 13)
The title compound was prepared in the same manner as in
Synthetic Example 4, using [G-4] 3-5, 10, 15-triphenyl-20- (4- methoxy-carbonylphenyl) porphyrin. XH NMR (CDCI3, ppm) :.δ 4.12 (s, 3H) , 4.75-4.69 (s, 168H) , 4.91
(s, 12H), 5.06 (s, 6H), 6.48 (t, 24H) , 6.52 (t, 12H) , 6.55 (t,
6H), 6.62 (t, 3H), 6.62 (d, 48H) , 6.65 (d, 24H) , 6.71 (d, 12H) ,
6.87 (d, 6H) , 7.19-7.38 (m, 252H) , 8.08 (m, 6H) , 8.39 (d, 2H) ,
8.52 (d, 2H), 8.95 (d, 6H) , 8.88 (d, 2H) [Reaction Scheme]
Figure imgf000028_0001
Synthetic Example 26: Preparation of ( [G-l] 3- [5, 10, 15- triphenyl-20- (4-methoxycarbonylphenyl) porphyrin] platinum) (Reaction Scheme 14) The title compound was prepared in the same manner as in Synthetic Example 5, using [G-l] 3-5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin.
XH NMR (CDC13, ppm) : δ 4.11 (s, 3H) , 5.11 (s, 12H) , 5.23 (s, 6H) , 6.68 (t, 3H) , 6.87 (d, 6H) , 7.30-7.46 (m, 36H) , 8.31 (m, 6H) , 8.39 (d, 2H) , 8.52 (d, 2H) , 8.95 (d, 6H) , 8.88 (d, 2H)
Synthetic Example 27: Preparation of ( [G-2 ] 3- [5, 10, 15- triphenyl-20- (4-methoxycarbonylphenyl) porphyrin] platinum)
(Reaction Scheme 14) The title compound was prepared in the same manner as in
Synthetic Example 5, using [G-2] 3-5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin.
2H NMR (CDCI3, ppm) : δ 4.12 (s, 3H) , 5.03 (s, 24H), 5.05 (s,
12H) , 5.25 (s, 6H) , 6.58 (t, 6H) , 6.63 (t, 3H) , 6.73 (d, 12H) , 6.86 (d, 6H), 7.23-7.40 (m, 66H) , 8.10 (m, 6H) , 8.39 (d, 2H) ,
8.52 (d, 2H) , 8.95 (d, 6H) , 8.88 (d, 2H)
Synthetic Example 28: Preparation of ( [G-3] 3- [5, 10, 15- triphenyl-20- (4-methoxycarbonylphenyl) porphyrin] platinum) (Reaction Scheme 14).
■ The title .compoun was prepared in the same manner as in Synthetic Example 5, using [G-3] 3-5, 10, 15-triphenyl-20- (4- ethoxycarbonylphenyl) porphyrin.
XH NMR (CDCI3, ppm) : δ 4.12 (s, 3H) , 4.95 (s, 72H) , 5.02 (s, 12H), 5.22 (s, 6H), 6.52 (t, 12H) , 6.55 (t, 6H) , 6.62 (t, 3H) ,
6.65 (d, 24H), 6.71 (d, 12H) , 6.87 (d, 6H) , 7.21-7.38 (m, 126H) , 8 . 08 (m, 6H) , 8 . 39 (d, 2H) , 8 . 52 (d, 2H) , 8 . 95 (d, 6H) , 8 . 88 ( d, 2H)
Synthetic Example 29: Preparation of ( [G-4] 3- [5, 10, 15- triphenyl-20- (4-methoxycarbonylphenyl) porphyrin] platinum) (Reaction Scheme 14)
The title compound was prepared in the same manner as in Synthetic Example 5, using [G-4] 3-5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin. XH NMR (CDC13, ppm) : δ 4.12 (s, 3H) , 4.75-4.69 (s, 168H) , 4.91 (s, 12H), 5.06 (s, 6H) , 6.48 (t, 24H) , 6.52 (t, 12H) , 6.55 (t, 6H) , 6.62 (t, 3H), 6.62 (d, 48H) , 6.65- (d, 24H) , 6.71 (d, 12H) , 6.'87 (d, 6H) , 7.19-7.38 (m, 252H) , 8.08 (m, 6H) , 8.39 (d, 2H) , 8.52 (d, 2H) , 8.95 (d, 6H) , 8.88 (d, 2H) [Reaction Scheme 14]
Figure imgf000030_0001
. Synthetic Example 30: Preparation of ( [G-l] 3-5, 10, 15- triphenyl-20- (4-carboxyphenyl) orphyrin) (Reaction Scheme 15) The title compound was prepared in the same manner as in Example 6, using [G-l] 3-5, 10, 15-triphenyl-20- (4- methoxycarbonyl) porphyrin. αH NMR (CDCI3, ppm) : δ -2.68 (s, 2H) , 5.11 (s, 12H) , 5.23 (s, 6H) , 6.68 (t, 3H) , 6.87 (d, 6H) , 7.30-7.46 (m, 36H) , 8.31 (m, 6H), 8.39 (d, 2H) , 8.52 (d, 2H) , 8.95 (d, 6H) , 8.88 (d, 2H) Synthetic Example 31: Preparation of ( [G-2] 3-5, 10, 15- triphenyl-20- (4-carboxyphenyl) porphyrin) (Reaction Scheme 15)
The title compound was prepared in the same manner as in Example 6, using [G-2] 3-5, 10, 15-triphenyl-20- (4- methoxycarbonyl) porphyrin.
XH NMR (CDC13, ppm) : δ -2.69 (s, 2H) , 5.03 (s, 24H) , 5.05 (s, 12H) , 5.25 (s, 6H), 6.58 (t, 6H) , 6.63 (t, 3H) , 6.73 (d, 12H) , 6.86 (d, 6H), 7.23-7.40 (m, 66H) , 8.10 (m, 6H) , 8.39 (d, 2H) , 8.52 (d, 2H) , 8.95 (d, 6H) , 8.88 (d, 2H)
Synthetic Example 32: Preparation of ( [G-3] 3-5, 10, 15- triphenyl-20- (4-carboxyphenyl) porphyrin) (Reaction Scheme 15) The title compound was prepared in the same manner as in Example 6, using [G-3] 3-5, 10, 15-triphenyl-20- (4-methoxycarbonyl) porphyrin. XH NMR (CDCI3, ppm) : δ -2.72 (s, 2H) , 4.95 (s, 72H) , 5.02 (s, 12H) , 5.22 (s, 6H), 6.52 (t, 12H) , 6.55 (t, 6H) , 6.62 (t, 3H) , 6.65 (d, 24H), 6.71 (d, 12H) , 6.87 (d, 6H) , 7.21-7.38 (m, 126H) , 8.08 (m, 6H) , 8.39 (d, 2H) , 8.52 (d, 2H) , 8.95 (d, 6H) , 8.88 (d, 2H)
Synthetic Example 33: Preparation of ( [G-4] 3-5, 10, 15- triphenyl-20- (4-carboxyphenyl) porphyrin) (Reaction Scheme 15)
The title compound was prepared in the same manner as in Example 6, using [G-4] 3-5, 10, 15-triphenyl-20- (4- methoxycarbonyl ) porphyrin.
XH NMR (CDCI3, ppm) : δ -2.72 (s, 2H) , 4.75-4.69 (s, 168H) , 4.91 (s, 12H), 5.06 (s, 6H), 6.48 (t, 24H) , 6.52 (t, 12H) , 6.55 (t, 6H) , 6.62 (t, 3H), 6.62 (d, 48H) , 6.65 (d, 24H) , 6.71 (d, 12H) , 6.87 (d, 6H), 7.19-7.38 (m, 252H) , 8.08 (m, 6H) , 8.39 (d, 2H) , 8.52 (d, 2H) , 8.95 (d, 6H) , 8.88 (d, 2H) [Reaction Scheme 15]
Figure imgf000032_0001
Synthetic Example 34: Preparation of ( [G-l ] 3- [5, 10, 15- triphenyl-20- (4-carboxyphenyl) porphyrin] zinc) (Reaction Scheme 16)
The title compound was prepared in the same as in Synthetic Example 6, using [G-l] 3- [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl ) porphyrin] zinc .
XH NMR (CDC13, ppm) : δ 5.11 (s, 12H) , 5.23 (s, 6H) , 6.68 (t, 3H) , 6.87 (d, 6H) , 7.30-7.46 (m, 36H) , 8.31 (m, 6H) , 8.39 (d, 2H) , 8.52 (d, 2H) , 8.95 (d, 6H) , 8.88 (d, 2H)
Synthetic Example 35: Preparation of ( [G-2 ] 3- [5, 10, 15- triphenyl-20- (4-carboxyphenyl) porphyrin] zinc) (Reaction Scheme
16)
The title compound was prepared in the same as in Synthetic
Example 6, using [G-2] 3- [5, 10, 15-triphenyl-20- (4- methoxycarbonylpήenyl) porphyrin] zinc . 1H NMR (CDCI3, ppm) : δ 5.03 (s, 24H),' 5.05 (s, 12H) , 5.25 (s,
6H), 6.58 (t, 6H) , 6.63 (t, 3H) , 6.73 (d, 12H) , 6.86 (d, 6H) ,
7.23-7.40 ( , 66H.) , 8.10 ( , 6H) , 8.39 (d, 2H) , 8.52 (d, 2H) ,
8.95 (d, 6H) , 8.88 (d, 2H)
Synthetic Example 36: Preparation of ( [G-3] 3- [5, 10, 15- triphenyl-20- (4-carboxyphenyl) porphyrin] zinc) (Reaction Scheme 16) The title compound was prepared in the same as in Synthetic Example 6, using [G-3] 3- [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] zinc.
2H NMR (CDC13, ppm) : δ- 4.95 (s, 72H) , 5.02 (s, 12H) , 5.22 (s, 6H) , 6.52 (t, 12H) , 6.55 (t, 6H) , 6.62 (t, 3H) , 6.65 (d, 24H) , 6.71 (d, 12H) , 6.87 (d, 6H) , 7.21-7.38 (m, 126H) , 8.08 ( , 6H) , 8.39 (d, 2H) , 8.52 (d, 2H) , 8.95 (d, 6H) , 8.88 (d, 2H)
Synthetic Example 37: Preparation of ( [G-4 ] 3- [5, 10, 15- triphenyl-20- (4-carboxyphenyl) porphyrin] zinc) (Reaction Scheme 16)
The title compound was prepared in the same as in Synthetic Example 6, using [G-4] 3- [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] zinc.
XH NMR (CDC13, ppm) : δ 4.75-4.69 (s, 168H) , 4.91 (s, 12H) , 5.06 (s, 6H) , 6.48 (t, 24H) , 6.52 (t, 12H) , 6.55 (t, 6H) , 6.62 (t, 3H) , 6.62 (d, 48H), 6.65 (d, 24H) , 6.71 (d, 12H) , 6.87 (d, 6H) , 7.19-7.38 (m, 252H) , 8.08 (m, 6H) , 8.39 (d, 2H) 52 ( d, 2H) 8.95 (d, 6H) , 8.88 (d, 2H)
[Reaction Scheme 16]
Figure imgf000033_0001
Synthetic Example 38: Preparation of ( [G-l] 3- [5, 10, 15- triphenyl-20- (4-carboxyphenyl) porphyrin] platinum) (Reaction
Scheme 17) The title compound was prepared in the same manner as in Synthetic Example 6, using [G-l] 3- [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] platinum.
1H NMR (CDC13, ppm) : δ 5.11 (s, 12H) , 5.23 (s, 6H) , 6.68 (t, 3H) , 6.87 (d, 6H) , 7.30-7.46 (m, 36H) , 8.31 (m, 6H) , 8.39 (d, 2H) , 8.52 (d, 2H) , 8.95 (d, 6H) , 8.88 (d, 2H)
Synthetic Example 39 : Preparation of ( [G-2 ] 3- [ 5 , 10 , 15- triphenyl-20- (4-carboxyphenyl) porphyrin] platinum) (Reaction Scheme , 17 )
The title compound was prepared in the same manner as in
Synthetic Example 6, using [G-2] 3- [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] platinum.
XH NMR (CDCI3, ppm) : δ 5.03 (s, ' 24H) , 5.05 (s, 12H) , 5.25 (s, 6H) , 6.58 (t, 6H) , 6.63 (t, 3H) , 6.73 (d, 12H) , 6.86 (d, 6H) ,
7.23-7.40 (m, 66H) , 8.10 (m, 6H) , 8.39 (d, 2H) , 8.52 (d, 2H) ,
8.95 (d, 6H), 8.88 (d, 2H)
Synthetic Example 40: Preparation of ( [G-3] 3- [5, 10, 15- triphenyl-20- (4-carboxyphenyl) porphyrin] platinum) (Reaction
Scheme 17)
The title compound was prepared in the same manner as in Synthetic Example 6, using [G-3] 3- [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] platinum. XH NMR (CDCI3, ppm) : δ 4.95 (s, 72H) , 5.02 (s, 12H) , 5.22 (s, 6H) , 6.52 (t, 12H) , 6.55 (t, 6H) , 6.62 (t, 3H) , 6.65 (d, 24H) , 6.71 (d, 12H), 6.87 (d, 6H) , 7.21-7.38 (m, 126H) , 8.08 ( , 6H) , 8.39 (d, 2H), 8.52 (d, 2H) , 8.95 (d, 6H) , 8.88 (d, 2H) Synthetic Example 41: Preparation of ( [G-4] 3- [5, 10, 15- triphenyl-20- ( 4-carboxyphenyl) porphyrin] platinum) (Reaction
Scheme 17)
The title compound was prepared in the same manner as in Synthetic Example 6, using [G-4] 3- [5, 10, 15-triphenyl-20- (4- methoxycarbonylphenyl) porphyrin] platinum.
XH NMR (CDC13, ppm) : δ 4.75-4.69 (s, 168H) , 4.91 (s, 12H) , 5.06 (s, 6H) , 6.48 (t, 24H), 6.52 (t, 12H) , 6.55 (t, 6H) , 6.62 (t, 3H), 6.62 (d, 48H), 6.65 (d, 24H) , 6.71 (d, 12H) , 6.87 (d, 6H) , 7.19-7.38 (m, 252H) , 8.08 (m, 6H) , 8.39 (d, 2H) , 8.52 (d, 2H) , 8.95 (d, 6H) , 8.88 (d, 2H)
[Reaction Scheme 17]
Figure imgf000035_0001
Synthetic Example 42: Preparation of 1- (4-carboxyphenyl) - naphthalene (Reaction Scheme 18)
1.00 g (4.58 mmol) of 1- (4-methylphenyl) -naphthalene [NA-1] and 1.16 g (7.33 mmol) of potassium permanganate were dissolved in 40 ml of a 7:3 mixture solution of pyridine and water. The solution was stirred for 24 hours at 120 °C and cooled to room temperature. The by-product Mn02 was filtered out and the crude product was adjusted to pH 1 by the addition of hydrochloric acid. The formed solid was washed several times with water to give 1- (4-carboxyphenyl) -naphthalene ( [NA-1] -C02H) . FT-IR (KBr, cm-1) : 3400-2200 (broad), 1683, 1607, 1419, 1293, 1111, 778. XH NMR (DMS0-d6, ppm) : 8.10 (d, 2H) , 8.02 (t, 2H) , 7.60 (d, IH), 7.58-7.45 (m, 6H) . El-Mass calcd. for Cι7Hι202: 248.08. Found: 248
[Reaction Scheme 18]
Figure imgf000036_0001
Synthetic Example 43: Preparation of [1- (4-carboxyphenyl) - 4- (4-methoxyphenyl) naphthalene] (Reaction Scheme 19)
The title compound was prepared in the same manner as in Synthetic Example 42 except that 1- (4-methylphenyl) -4- (4- methoxyphenyl) naphthalene [NA-2] was used instead of l-(4- methylphenyl) -naphthalene [NA-1] .
FT-IR (KBr, cm-1) : 3300-2200 (very broad), 2928, 1682, 1436, 1247, 1119, 824, 722. XH NMR (DMSO-d6, ppm) : 8.16 (d, 2H) , 7.87 (t, 2H) , 7.51-7.42 (m, 8H) , 7.12 (d, 2H) , 3.85 (s, 3H) ; El-Mass calcd. for C4Hi8θ3: 354.13. Found: 354
[Reaction Scheme 19]
Figure imgf000036_0002
Synthetic Example 44: Preparation of 9- (4-carbonylphenyl) - 10- (4-methoxyphenyl) anthracene (Reaction Scheme 20) The title compound was prepared in the same manner as in Synthetic Example 42 except that 1- (4-methylphenyl) -4- (4- methoxyphenyl) anthracene [AN-1] was used instead of l-(4- methylphenyl) -naphthalene [NA-1] . FT-IR (KBr, cιrf ) 3300-2200 (very broad), 2925, 1683, 1600,
1508, 1238, 1119, 825, 724. XH NMR (DMSO-d6, ppm) : 7.93 (d, 2H) , 7.78 (m, 2H), 7.62 (d, 2H) , 7.54 (m, 2H) , 7.40-7.34 (m, 6H) , 7.16 (d, 2H) , 3.97 (s, 3H) El-Mass calcd. for C28H2o03: 404.14. Found: 404
[Reaction Scheme 20]
Figure imgf000037_0001
Synthetic Example 45: Preparation of [NA-3]2-C02H (Reaction Scheme 21)
As shown in Reaction Scheme 21 below, 1.90 g (2.34 mmol) of [NA-3]2-C02Me and 1.05 g (18.70 mmol) of KOH were dissolved in 26 ml of a 10:3 mixture solution of ethanol and water. The solution was stirred for 4 hours at 120 °C and then cooled to room temperature. The reaction product was adjusted to pH 1 by the addition of hydrochloric acid. The formed solid was washed several times with water to give [NA-3]2-C02H.
FT-IR (KBr, cm"1) : 3300-2100 (very broad), 1690, 1510, 1250, 1160, 830, 760. XH NMR (DMSO-d6, ppm) : 7.91 (m, 4H) , 7.63 (d, 4H) , 7.56-7.42 (m, 16H) , 7.27 (d, 2H) , 7.12 (d, 2H) , 7.07 (t, IH) , 5.30 (s, 4H) , 3.85 (s, 6H) . El-Mass calcd. for C55H206: 798.30. Found: 798.
[Reaction Scheme 21]
Figure imgf000038_0001
[NA-3]2-C02Me [NA-3]2-C02H
Synthetic Example 46: Preparation of [AN-2]2-C02H (Reaction Scheme 22)
As shown in Reaction Scheme 22 below, [AN-2]2-C02H was prepared in Synthetic Example 45 except that [AN-2]2-C02Me was used instead of [NA-3] 2-C02Me.
FT-IR (KBr, cm"1) : 3300, 1690 (vc„0) , 1246 (vc_0) . XH NMR (DMSO-d6, ppm) : 8.05 (m, 4H) , 7.53-7.45 (m, 26H) , 7.12 (d, 4H) , 7.03 (m, IH) , 5.22 (s, 4H) , 3.91 (s, 6H)
[Reaction Scheme 22]
Figure imgf000038_0002
[AN-2]2-C02Me [AN-2]2-C02H
Synthetic Example 47: Preparation of [G-l]- [NA-2] -CQ2H (Reaction Scheme 23)
The title compound was prepared in the same manner as in Synthetic Example 42 except that [G-l] -[NA-2] was used instead of [NA-1] .
FT-IR (KBr, cm"1) : 3300-2200 (very broad), 3028, 2922, 1692, 1595, 1448, 1166, 1030, 741. XH NMR (CDC13, ppm) : 8.10 (m, IH) , 7.81 (m, 2H), 7.66 (m, 2H) , 7.48-7.33 (m, 17H) , 7.12 (d, 2H) , 6.87 (d, 2H) , 6.68 (t, IH) , 5.10 (s, 2H) , 5.04 (s, 4H) ; El-Mass calcd. for C44H34O5: 642.24. Found: 642 [Reaction Scheme 23]
Figure imgf000039_0001
[G-1]-[NA-2] [G-1]-[NA-2]-C02H
Synthetic Example 48: Preparation of [G-2] - [NA-2] -CQ2H (Reaction Scheme 24)
The title compound was prepared in the same manner as in Synthetic Example 42 except that [G-2] -[NA-2] was used instead of [NA-1] . FT-IR (KBr, cm"1) : 3300-2200 (very broad), 3032, 2920, 1692, 1596, 1448, 1162, 1030, 740. XH NMR (CDC13, ppm) : 8.14 (m, IH) , 7.82 (m, 2H) , 7.66 ( , 2H) , 7.48-7.31 (m, 27H) , 7.12 (d, 2H) , 6.74 (d, 2H) , 6.70 (d, 4H) , 6.58 (t, 3H) , 5.09 (s, 2H) , 5.04 (s, 8H) , 5.00 (s, 4H) ; FAB-Mass calcd. for C72H5809: 1066.41. Found: 1066
[Reaction Scheme 24 ]
Figure imgf000039_0002
Synthetic Example 49: Preparation of [G-3] - [NA-2] -CQ2H
(Reaction Scheme 25)
The title compound was prepared in the same manner as in Synthetic Example 42 except that [G-3] -[NA-2] was used instead of [NA-1] . FT-IR (KBr, cm"1) ' : 3300-2200 (very broad), 3032, 2920, 1692, 1596,' 1448, 1162, 1030, 742. XH NMR (CDC13, ppm) : 8.14 (m, IH) , 7.82 (m, 2H) , 7.65 ( , 2H) , 7.52-7.31 (m, 47H) , 7.12 (d, 2H) , 6.85 (d, 4H) , 6.78 (d, 8H), 6.74 (m, 6H) , 6.62 (t, 3H) , 5.07 (s, 2H), 5.02 (s, 16H), 4.96 (s, 12H) ; FAB-Mass calcd. for C128H106θι7: 1914.74. Found: 1914
[Reaction Scheme 25]
Figure imgf000040_0001
Synthetic Example 50: Preparation of [G-4] - [NA-2] -C02H (Reaction Scheme 26)
The title compound was prepared in the same manner as in Synthetic Example 42 except that [G-4] -[NA-2] was used instead of [NA-1] .
FT-IR (KBr, cm"1) : 3300-2200 (very broad), 3028, 2925, 1693, 1593, 1452, 1165, 1031, 740. 2H NMR (CDC13, ppm) : 8.12 (m, IH) , 7.83 (m, 2H), 7.67 (m, 2H) , 7.52-7.31 (m, 87H) , 7.11 (d, 2H) , 6.86 (d, 8H) , 6.78 (d, 16H) , 6.76 (m,' 18H) , 6.65 (t, 3H) , 5.09 (s, 2H) , 5.04 (s, 32H) , 4.97 (s, 28H) ; FAB-Mass calcd. for C240H202θ33 3611.41. Found: 3611
[Reaction Scheme 26]
Figure imgf000041_0001
Synthetic Example 51: Preparation of [G-l] - [AN-1] -C02H (Reaction Scheme 27)
The title compound was prepared in the same manner as in Synthetic Example 42 except that [G-l] -[AN-1] was used instead of [NA-1] .
FT-IR (KBr, cm"1) : 3300-2200 (very broad), 3025, 2920, 1693, 1592, 1447, 1162, 1032, 742. XH NMR (CDC13, ppm) : 7.92 (d, 2H) , 7.98 (dd, 2H) , 7.63 (d, 2H) , 7.54 (dd, 2H) , 7.48-7.33 (m, 16H) , 7.16 (d, 2H) , 6.76 (d, 2H) , 6.58 (t, IH) , 5.09 (s, 2H) , 5.02 (s, 4H) ; El-Mass calcd. for C48H36O5: 692.26. Found: 692
[Reaction Scheme 27]
Figure imgf000041_0002
[G-1]-[AN-1] [G-1]-[AN-1]-C02H
Synthetic Example 52: Preparation of [G-2] - [AN-1] -CQ2H (Reaction Scheme 28)
The title compound was prepared in the same manner as in Synthetic Example 42 except that [G-2] -[AN-1] was used instead of [NA-1] . FT-IR (KBr, CIT ,L-l )\ : 3300-2200 (very broad), 3032, 2920, 1692, 1596, 1448, 1162, 1030, 740. XH NMR (CDC13, ppm) : 7.92 (d, 2H) , 7.79 (dd, 2H) , 7.62 (d, 2H) , 7.54 (dd, 2H) , 7.48-7.32 (m, 26H) , 7.16 (d, 2H), 6.77 (d, 2H) , 6.71 (d, 4H) , 6.59 (t, 3H) , 5.13 '(s, 2H) , 5.04 (s, 8H) , 5.02 (s, 4H) ; El-Mass calcd. for C76H60O9: 1116.42. Found: 1116
[Reaction Scheme 28]
Figure imgf000042_0001
Synthetic Example 53: Preparation of [G-3] - [AN-1] -CQ2H (Reaction Scheme 29)
The title compound was prepared in the same manner as in Synthetic Example 42 except that [G-3] -[AN-1] was used instead of [NA-1] .
FT-IR (KBr, cm"1) : 3300-2200 (very broad), 3032, 2920, 1692, 1596, 1448, 1162, 1030, 740. XE NMR (CDC13, ppm) : 7.92 (d, 2H) , 7.80 (dd, 2H), 7.60 (d, 2H) , 7.53 (dd, 2H) , 7.48-7.32 (m, 46H) , 7.16 (d, 2H)., 6.85 (d, 4H) , 6.77 (d, 8H) , 6.72 (m, 6H) , 6.62 (t, 3H) , 5.09 (s, 2H) , 5.04 (s, 16H) , 4.97 (s, 12H) ; FAB-Mass calcd. for Cα32H108Oι7 : 1964.76. Found: 1964
[Reaction Scheme 29]
Figure imgf000043_0001
Synthetic Example 54: Preparation of- [G-4]- [AN-1] -CQ2H (Reaction Scheme 30)
The title compound was prepared in the same manner as in Synthetic Example 42 except that [G-4] -[AN-1] was used instead of [NA-1].
FT-IR (KBr, cm"1) : 3300-2200 (very broad), 3032, 2921, 1694, 1594, 1447,- 1160, 1033, 743. XH NMR (CDC13, ppm) : 7.92 (d, 2H) , 7.79 (dd, 2H), 7.61 (d, 2H) , 7.52 (dd, 2H) , 7.48-7.30 ( , 86H) , 7.14 (d, 2H) , 6.86 (d, 8H) , 6.78 (d, 16H) , 6.76 (m, 18H) , 6.65 (t, 3H) , 5.09 (s, 2H) , 5.04 (s, 32H) , 4.97 (s, 28H) ; FAB-Mass' calcd. for C24H2o033: 3661.43 Found: 3661
[Reaction Scheme 30]
Figure imgf000043_0002
■ Synthetic Example 55: Preparation of [G-l] - [NA-3] 2-CQ2H (Reaction Scheme 31)
The title compound was prepared in the same manner as in Synthetic Example 45 except that [G-l] - [NA-3] 2-C02Me was used instead of [NA-3] 2-C02Me.
XH NMR (CDC13, ppm) : 7.92 (m, 4H) , 7.62 (d, 4H) , 7.56-7.32 (m, 36H), 7.26 (d, 2H) , 7.12 (d, 4H) , 7.07 (t, IH) , 6.76 (d, 4H) , 6.58 (t, 2H) , 5.30 (s, 4H) , 5.09 (s, 4H) , 5.02 (s, 8H) [Reaction Scheme 31]
Figure imgf000044_0001
[G-1]-[NA-3]2-CO2Me [G-1]-[NA-3]2-CO2H '= [G-1]
.Synthetic Example 56: Preparation of [G-2] - [NA-3] 2-C02H (Reaction Scheme 32)
The title compound was prepared in the same manner as in Synthetic Example 45 except that [G-2] - [NA-3] 2-C02Me was used instead of [NA-3] 2-C02Me.
XE NMR (CDCI3, ppm) : • 7.92 (m, 4H) , 7.62 (d, 4H) , 7.52-7.32 (m, 56H), 7.24 (d, 2H) , 7.11 (d, 4H) , 7.08 (t, IH) , 6.74 (d, 4H) , 6.70 (d, 8H) , 6.58 (t, 6H) , 5.31 (s, 4H) , 5.09 (s, 4H) , 5.04 (s,' 16H), 4.98 (s, 8H)
[Reaction Scheme 32]
Figure imgf000045_0001
[G-2]-[NA-3]2-CO2Me [G-2]-[NA-3]2-CO2H
R'= [G-2]
Synthetic Example 57: Preparation of [G-3] - [NA-3] 2-CQ2H (Reaction Scheme 33)
The title compound was prepared in the same manner as in Synthetic Example 45 except that [G-3] - [NA-3] 2-C02Me was used instead of [NA-3]2-C02Me.
XH NMR (CDC13, ppm) : 7.92 (m, 4H) , 7.62 (d, 4H) , 7.52-7.32 (m, 96H), 7.24 (d, 2H), 7.11 (d, 4H) , 7.08 (t, IH) , 6.87. (d, 8H) , 6.79 (d, 16H) , 6.71 ( , 12H) , 6.63 (t, 6H) , 5.30 (s, 4H) , 5.10 (s, 4H) , 5.03 (s, 32H) , 4.99 (s, 24H)
[Reaction Scheme 33]
Figure imgf000045_0002
[G-2]-[NA-3]2-CO2Me [G-2]-[NA-3]2-CO2H
R'= [G-3]
Synthetic Example 58: Preparation of [G-4] - [NA-3] 2-C02H (Reaction Scheme 34) The title compound was prepared in the same manner as in Synthetic Example 45 except that [G-4] - [NA-3] 2-C02Me was used instead of [NA-3] 2-C02Me.
XH NMR (CDC13, ppm) : 7.92 (m, 4H) , 7.62 (d, 4H) , 7.52-7.32 (m, 176H), 7.24 (d, 2H), 7.11 (d, 4H) , 7.08 (t, IH) , 6.85 (d, 16H) , 6.79 (d, 32H) , 6.73 .(m, 36H) , 6.62 (t, 6H) , 5.30 (s, 4H) , 5.09 (s, 4H) , 5.04 (s, 64H) , 4.97 (s, 56H)
[Reaction Scheme 34] •
Figure imgf000046_0001
R'= [G-4]
Synthetic Example 59: Preparation of [G-l] - [AN-2] -C02H
(Reaction Scheme 35) The title compound was prepared in the same manner as in
Synthetic Example 46 except that [G-l] - [AN-2] -C02Me was used instead of [AN-2] 2-C02Me . αH NMR (CDCI3, ppm) : 7.95 (d, 4H) , 7.98 (dd, 4H) , 7.63 (d, 4H) ,
7.54 (dd, 4H) , 7.52-7.32 (m, 36H) , 7.26 (d, 2H) , 7.12 (d, 4H) , 7.07 (t, IH) , 6.74 (d, 4H) , 6.53 (t, 2H) , 5.22 (s, 4H) , 5.09 (s,
4H) , 5.02 (s, 8H)
[Reaction Scheme 35]
Figure imgf000047_0001
[G-1]-[NA-3]2-CO2 e [G-1]-[NA-3]2-CO2H
R'= [G-1]
Synthetic Example 60: Preparation of [G-2] - [AN-2] -CQ2H (Reaction Scheme 36)
The title compound was prepared in the same manner as in Synthetic Example 46 except that [G-2] - [AN-2] -C02Me was used instead of [AN-2] 2-C02Me.
XH NMR (CDC1 , ppm) : 7.95 (d, 4H) , 7.96 (dd, 4H) , 7.65 (d, 4H) , 7.54 (dd, 4H) , 7.49-7.30 (m, 56H) , 7.26 (d, 2H) , 7.11 (d, 4H) , 7.08 -(t, IH) , 6.77 (d, 4H) , 6.69 (d, 8H) , 6.55 (t, 6H) , 5.31 (s, 4H), 5.11 (s, 4H) , 5.06 (s, 16H) , 4.97 (s, 8H)
[Reaction Scheme 36]
Figure imgf000047_0002
[G-2]-[AN-2]2-CO2Me [G-2]-[AN-2]2-CO2H
R'= [G-2]
Synthetic Example 61: Preparation of [G-3] - [AN-2] -CQ2H (Reaction Scheme 37)
The title compound was prepared in the same manner as in Synthetic Example 46 except that [G-3] - [AN-2] -C02Me was used instead of [AN-2] 2-C02Me. XH NMR (CDCI3, ppm) : 7.97 (d, 4H) , 7.95 (dd, 4H) , 7.66 (d, 4H) , 7.54 (dd, 4H) , 7.50-7.30 (m, 96H) , 7.26 (d, 2H) , 7.10 (d, 4H)-, 7.09 (t, IH) , 6.87 (d, 8H) , 6.79 (d, 16H) , 6.72 (m, 12H) , 6.63 (t, 6H) , 5.32 (s, 4H) , 5.11 (s, 4H) , 5.05 (s, 32H) , 4.98 (s, 24H)
[Reaction Scheme 37]
Figure imgf000048_0001
[G-2]-[AN-2]2-CO2Me [G-2]-[AN-2]2-C02H
R* = [G-3]
Synthetic Example 62: Preparation of [G-4]- [AN-2] -CQ2H (Reaction Scheme 38)
The title compound was prepared in the same manner as in Synthetic Example 46 except that [G-4] - [AN-2] -C02Me was used instead of [AN-2] 2-C02Me.
XH NMR (CDCI3, ppm) : 7.99 (d, 4H) , 7.94 (dd, 4H) , 7.65 (d, 4H) , 7.54 (dd, 4H) , 7.50-7.30 (m, 176H), 7.26 (d, 2H) , 7.10 (d, 4H) , 7.09 (t, IH) , 6.85 (d, 16H) , 6.79 (d, 32H) , 6.73 ( , 36H) , 6.62
(t, 6H) , 5.30 (s, 4H) , 5.10 4H) , 5.07 (s, 64H), 4.99 (s, 56H)
[Reaction Scheme 38]
Figure imgf000049_0001
[G-4]-[AN-2]2-CO2 e [G-4]-[AN-2]2-CO2H
R' = [G-4]
Examples
Example 1 : Preparation of Yb3+- (C6H5COO~) 3 (Reaction Scheme
39 )
Into a flask which had been sufficiently dried under vacuum, 108 mg (2.7 mmol) of KH was charged under a nitrogen stream. Into another flask, 300 mg (2.46 mmol) of benzoic acid was charged, and dissolved in 25 ml of THF. This solution was charged into the KH-containing flask by a cannula, and stirred until hydrogen, gas was not generated. 5 ml of THF and 5 ml of EtOH were added to 229 mg (0.82 mmol) of anhydrous YbCl3. This solution was added to the potassium salt-containing mixture by a cannula and stirred for one day. After the solvent was removed under vacuum, the crude product was dried, washed several times with hexane and dried in vacuum to give the title compound. Er3+- (C6H5COO~)3 and Nd3+- (C6H5COO") 3 were also prepared in the same manner. FT-IR (KBr, cm"1) : 1604, 1418. Yb3+- (C6H5COO")3 : λem = 976 nm (λex = 325 nm, solid state) Er3+- (C6H5COO")3 : λem = 1540 nm (λex = 325 nm, solid state) Nd3+-(C6H5COO")3 : λem = 886, 1054, 1325 nm (λex = 325 nm, solid state)
Example 2: Preparation of Yb3+- (C6F5COO") 3 (Reaction Scheme 39) The title compound was prepared in the same manner as in Example 1 except that pentafluorobenzoic acid was used instead of benzonic acid. Also, Er3+- (C6F5COO") 3 and Nd3+- (C6F5COO") 3 were prepared in the same manner. FT-IR (KBr, cm-1) : 1617, 1409.
Yb ,3+ - ( C6F5COO") 3 : λem = 976 nm (λe 325 nm, solid state )
Er .3J+-(C6F5COO")3 : λs 1540 nm (λex = 325 nm, solid state)
Ndj3+- (C6F5COO")3 : λem = 886, 1054, 1325 nm (λex = 325 nm, solid state)
[Reaction Scheme 39]
Figure imgf000050_0001
Ra is H or F
Example 3: Preparation of Yb3"1"- (CgHsCOO")^ (bipyridine) (Reaction Scheme 40)
The title compound was prepared in the same manner as in Example 1, using benzoic acid with the addition of anhydrous YbCl3 and 128 mg (0.82 mmol) of bipyridine. Also, Er3+- (C6H5COO") 3 (bipyridine) and Nd3+- (C6H5COO~) 3 (bipyridine) were prepared in the same manner. FT-IR (KBr,- cm"1) : 1600, 1412.
Yb3+- (C6H5COO") 3 (bipyridine) λem = 976 nm (λex = 325 nm, solid state)
Er3+- (C6H5COO") 3 (bipyridine) λe = 1530 nm (λex = 325 nm, solid state)
Nd3+- (C6H5COO") 3 (bipyridine) λem = 884, 1055, 1324 nm (λex =
325 nm, solid state) Example 4: Preparation of Yb,3+- (CβFsCOO") 3 (bipyridine) (Reaction Scheme 40)
The title compound was prepared in the same manner as in Example 3 except that pentafluorobenzoic acid was used instead of benzoic acid. Also, Er3+- (C6F5COO~) 3 (bipyridine) 2 and Nd3+- (C6F5COO")3 (bipyridine) were prepared in the same manner. - FT-IR (KBr, cm"1) : 1587, 1395.
Yb3+- (C6F5COO") 3 (bipyridine) λem = 976 nm (λex = 325 nm, solid state)
Er3+- (C6F5COO") 3 (bipyridine) λe = 1517 nm (λex = 325 nm, solid state)
Nd3+- ( C6F5COO") 3 (bipyridine) λem = 884 , 1055 , 1324 nm (λex. =
325 nm, solid state )
[Reaction Scheme 40]
Figure imgf000051_0001
Ra is H or F
Example 5 : Yb .3+ - ( [NA-1 ] -C02 ) 3 ( terpyridine ) .(Reaction Scheme 41 ]
Into a flask which had been dried under vacuum, 56 mg (1.40 mmol) of KH, 300 mg (1.21 mmol) of [NA-1]-C02H and 100 mg (0.42mmol) of terpyridine were charged under a nitrogen stream. The mixture was dissolved in 100 ml of THF and stirred until hydrogen gas was not generated. In another flask, a small amount of methanol was added to 113 mg (0.40 mmol) of anhydrous YbCl3. This solution was added to the potassium salt-containing mixture by a cannula and stirred for one day. After the solvent was removed under vacuum, the residue was dried, washed several times with diethyl ether and dried in vacuum to give the title compound. Er3+- ( [NA-1] -C02 ") 3 (terpyridine) and Nd3+- ( [NA-1] -C02 ") 3
(terpyridine) were also prepared in the same manner.
Yb3+- ( [NA-1] -C02 ~) 3 (terpyridine) λem = 972 n (λex = 325 nm, solid state)
Er3+-( [NA-1] -C02 ") 3 (terpyridine) λem = 1530 nm (λex = 325 nm, solid state) ( [NA-1] -C02 ") 3 (terpyridine) λP = '888, 1053, 1324 nm (λex = 325 nm, solid state) [Reaction Scheme 41]
Figure imgf000052_0001
[NA-1]-C02H Er3+-([NA-1]-C02 ")3(terpyridine)
Example 6: Preparation of Yb3+- ( [NA-2] -C02 ") 3 (terpyridine) (Reaction Scheme 42)
The title compound was prepared in the same manner as in Example 5 except that [NA-2]-C02H was used instead of [NA-1]-C02H. Also, Er3+-( [NA-2] -C02 ") 3 (terpyridine) and Nd3+- ( [NA-2] -C02 ") 3 (terpyridine) were prepared in the same manner. Yb3+- ( [NA-2] -C02 ") 3 (terpyridine) λem = 975 nm (λex = 325 nm, solid state) Er3+- ( [NA-2] -C02 ") 3 (terpyridine) λ, = 1530 nm (λex = 325 nm, solid state)
Nd3+- ( [NA-2] -C02 ") 3 (terpyridine) λem = 885, 1053, 1324 nm (λex = 325 nm, solid state) [Reaction Scheme 42]
Figure imgf000053_0001
[NA-2]-C02H LnJ+-(tNA-2]-C02-)3(terpyridine)
Example 7: Preparation of Yb3+- ( [NA-3] 2-CQ2 ~) 3 (terpyridine) (Reaction Scheme 43)
The title compound was prepared in the same manner as in Example 5 except that ( [NA-3] ) 2-C02H was used instead of [NA-1]- C02H. Also, Er3+-( [NA-3] 2-C02 ") 3 (terpyridine) and Nd3+- ( [NA-3] -C02 ~ )3 (terpyridine) were prepared in the same manner. Yb3+-( [NA-3] 2-C02 ") 3 (terpyridine) : λem = 975 nm (λex = 325 nm, solid state)
Er3+- ( [NA-3] 2-C02 ") 3 (terpyridine) λP 1530 nm (λex = 325 nm, solid state)
Nd3+- ( [NA-3] 2-C02 ~) 3 (terpyridine) λ. = 885, 1054, 1323 nm (λex = 325 nm, solid state) [Reaction Scheme 43]
Figure imgf000053_0002
Figure imgf000053_0003
Ln3+-([NA-3]2-C02-)3(terpyridine)
Example 8: Preparation of Yb3+- ( [NA-1] -C02 ~) 3 (bipyridine) (Reaction Scheme 44)
The title compound was prepared in the same manner as in Example 5 except that bipyridine was used instead of terpyridine. Also, Er3+-([NA-1]-C02 ")3 (bipyridine) and Nd3+- ( [NA-1] -C02 "~) 3 (bipyridine) were prepared in the same manner.
Yb3+- ( [NA-1] -C02 ~) 3 (bipyridine) λem = 976 nm (λex = 325 nm, solid state)
Er3+- (■ [NA-1] -C02 ~) 3 (bipyridine) λem = 1530 nm (λex = 325 nm, solid state)
Nd3+- ( [NA-1] -C02 ~) 3 (bipyridine) λe 885, 1055, 1323 nm (λε
= 325 nm, solid state)
[Reaction Scheme 44]
Figure imgf000054_0001
[NA-1]-C02H Ln ,3°+-([NA-1]-C02-)3(Bipyridine)
'Example 9: Preparation of Yb ,3J+ - ( [NA-2] -C02 ") 3 (bipyridine) (Reaction Scheme 45)
The title compound was prepared in the same manner as in Example 5 except that bipyridine was used instead of terpyridine. Also, Er3+- ( [NA-2] -C02 ") 3 (bipyridine) and Nd3+- - ( [NA-2] -C02 ") 3 (bipyridine) were prepared in the same manner.
Yb3+- ( [NA-2]-C02 ) 3 (bipyridine) λem = 975 nm (λex = 325 nm, solid state)
Er3+- ( [NA-2] -C02 ") 3 (bipyridine) λe = 1530 nm (λex = 325 nm, solid state)
Nd3+- ( [NA-2] -C02 ") 3 (bipyridine) λem = 885, 1053, 1323 nm (λex
= 325 nm, solid state)
[Reaction Scheme 45]
Figure imgf000055_0001
Figure imgf000055_0002
Ln ,3"1+ -([NA-2]-C02-)3(Bipyιϊdirιe)
Example 10: Preparation of Yb3+- ( [NA-3] -C02 )3 (bipyridine) (Reaction Scheme 46)
The title' compound was prepared in the same manner as in Example 5 except that bipyridine was used instead of terpyridine. Also, Er3+-( [NA-3]-C02 ")3 (bipyridine) ' and Nd3+- ( [NA-3] -C02 ") 3 (bipyridine) were prepared in the same manner. Yb3+- ( [NA-3] 2-C02 ~) 3 (bipyridine) λP = 975 nm (λex = 325 nm, solid. state)
Er3+- ( [NA-3] 2-C02 ") 3 (bipyridine) λem = 1532 nm (λex == 325 nm, solid state)
Nd 3+ ( [NA-3] 2-C02 ) 3 (bipyridine) : λe 885, 1053, 1323 nm (λe
= 325 nm, solid state)
[Reaction Scheme 46]
Figure imgf000055_0003
[NA-3]2-C02H Ln3+-([NA-3]2-C02-)3(Bipyridine)
Example 11: Preparation of Yb .3+- ( [AN-1] -C02 ") 3 (terpyridine) (Reaction Scheme 47)
The title compound was prepared in the same manner as in Example 5 except that [AN-1]-C02H was used instead of [NA-1]-C02H. Also, Er -3++-( [AN-1]-C02 )3 (terpyridine) and Nd3+- ( [AN-1] -C02 " (terpyridine) were prepared in the same manner.
Yb3+- ( [AN-1] -C02 ") 3 (terpyridine) λem = 976 nm (λex = 442 nm, solid state)
Er3+- ( [AN-1] -C02 ") 3 (terpyridine) λem = 1531 nm (λex = 442 nm, solid state)
Nd3+- ( [AN-1] -C02 ") 3 (terpyridine) λem = 885, 1055, 1324 nm (λex = 442 nm, solid state) [Reaction Scheme 47]
Figure imgf000056_0001
[AN-1]-C02H Ln ,3°+ -([AN-1]-C02-)3(te yridine)
Example 12: -Preparation of Yb3+- ( [AN-2] -C02 ") 3 (terpyridine) (Reaction Scheme 48)
The title compound was prepared in the same manner as in Example 5 except that [AN-2]-C02H was used instead, of [AN- 1]-C02H. Also, Er3+-( [AN-2] -C02 ~) 3 (terpyridine) and Nd3+- ( [AN- 2]-C02 ~)3 (terpyridine) were prepared in the same manner. Yb3+-C [AN-2] 2-C02 ") 3 (terpyridine) λem = 976 nm (λe 442 nm, solid state)
Er3+- ( [AN-2 ] 2-C02 " ) 3 (terpyridine ) λem = 1531 nm (λex = 442 nm, solid state)
Nd3+- ( [AN-2] 2-C02 ") 3 (terpyridine) λp = 885, 1055, 1324 nm (λex = 442 nm, solid state) [Reaction Scheme 48]
Figure imgf000057_0001
Figure imgf000057_0002
Ln3+-([AN-2]2-C02-)3(terpyιϊdine)
■Example 13: Preparation of Yb3+- ( [AN-1] -CQ2 ~) 3 (bipyridine) (Reaction Scheme 49)
The title compound was prepared in the same manner as in Example 5 except that [AN-1]-C02H was used instead of [NA-1]-C02H, and terpyridine was used instead of bipyridin. Also, Er3+- ( [AN- 1]-C02 ~) 3 (bipyridine) and Nd3+- ( [AN-1] -C02 ~) 3 (bipyridine) were prepared in the same manner.
Yb3+- ( [AN-1 ] -C02 ~) 3 (bipyridine) λΘm = 975 nm (λex = 442 nm, solid state )
Er3+- ( [AN-1] -C02 ") 3 (bipyridine ) λem = 1530 nm (λex = 442 nm, solid state)
Nd3+- ( [AN-1 ] -C02 ~) 3 (bipyridine) Λ-em — 14 , 1053 , 1324 nm (λe
= 442 nm, solid state )
[Reaction Scheme 49]
Figure imgf000057_0003
[AN-1]-C02H Li ,T3+-([AN-1]-C02")3(Bipyridine)
Example 14: Preparation of Yb3+- ( [AN-2] 2-C02 ") 3 (bipyridine) (Reaction Scheme 50)
The title compound was prepared in the same manner as in Example 5 except that [AN-2]2-C02H was used instead of [AN-1]2- C02H, and bipyridine was used instead of terpyridine . Also, Er .3' + ( [AN-2] 2-C02 ") 3 (bipyridine) and Nd3+- ( [AN-2] 2-C02 ") 3 (bipyridine) were prepared in the same manner . Yb3+- (. [AN-2 ] 2-C02 ") 3 (bipyridine) λe = 975 nm (λex = 442 nm, solid state )
Er3+- ( [AN-2 ] 2-C02 ") 3 (bipyridine) λem = 1530 nm (λex = 442 nm, solid state )
[Reaction Scheme 50]
Figure imgf000058_0001
[AN-2]2-C02H Ln3+-([AN-2]2-C02-)3(Bipyridine)
- Example 15 : Preparation of Yb 3+- ( [G-l] - [NA-2] -C02 ") 3
(terpyridine) (Reaction Scheme 51)
The title compound was prepared in the same manner as in Example 5 except that [G-l] - [NA-2] -C02H was used instead of [NA- 1]-C02H. Also, Er3+-( [G-l] -[NA-2] -C02 ") 3 (terpyridine) and Nd3+- ( [G-l] - [NA-2] -CO2 ") 3 (terpyridine) are prepared in the same manner.
Yb3+- ( [G-l ] - [NA-2 ] -C02 ") 3 (terpyridine ) λem = 976 nm (λe 325 n , solid state)
Er3+- ( [G-l ] - [NA-2 ] -C02 ") 3 (terpyridine) - λem = 1530 nm (λe 325 nm, solid state)
Nd3+- ( [ [G-l] - [NA-2] -C02 "] 3 (terpyridine) λem = 886, 1053 , 1324 nm (λex = 325 nm, solid state) [Reaction Scheme 51]
Figure imgf000059_0001
[G-1]-[NA-2]-C02H Ln^-([G-1]-[NA-2]-C02-)3(terpyridine)
R'= [G-1]
Example 16: Preparation of Yb 3+- ( [G-2] - [NA-2] -CQ2 ") 3 (terpyridine) (Reaction Scheme 52)
The title compound was prepared in the same manner as in Example 5 except that [G-2] - [NA-2] -C02H was used instead of [NA-' 1]-C02H. Also, Er3+-([G-2]-[NA-2]-C02 ")3 (terpyridine) and Nd3+- ( [G-2] - [NA-2] -C02 ~) 3 (terpyridine) were prepared in the same manner.
Yb3+- ( [G-2] - [NA-2] -C02 ") 3 (terpyridine) λP = 975 nm (λex = 325 nm, solid state)
Er3+- ( [G-2] - [NA-2] -C02 ~) 3 (terpyridine) λP 1530 nm (λex = 325 nm, solid state) Ndj3+-( [G-2] -[NA-2] -C02 ") 3 (terpyridine) : λem = 886, 1054, 1324 nm (λex = 325 nm, solid state) [Reaction Scheme 52]
Figure imgf000059_0002
[G-1]-[NA-2]-C02H Ln ,3*+ -([G-1MNA-2]-C02 _)3(terpyridine)
R1 = [G-2]
Example 17: Preparation of Yb .3J+^- ( [G-3] - [NA-2] -C02 ") 3 (terpyridine) (Reaction Scheme 53) The title compound was prepared in the same manner as in Example 5 except that [G-3] - [NA-2] -C02H was used instead of [NA- 1]-C02H. Also, Er3+-( [G-3] -[NA-2] -C02 ~)3 (terpyridine) and Nd3+- ( [G-3] - [NA-2] -C02 ") 3 (terpyridine) were prepared in the same manner.
Yb3+- ( [G-3] - [NA-2] -C02 ") 3 (terpyridine) λe = 976 nm (λe 325 nm, solid state)
Er3+- ( [G-3] - [NA-2] -C02 ") 3 (terpyridine) λem = 1530 nm (λex = 325 nm, solid state)
Nd3+- (-[G-3] - [NA-2] -C02 ") 3 (terpyridine) λe 886, 1053, 1324 nm (λex = 325 nm, solid state) [Reaction Scheme 53]
Figure imgf000060_0001
[G-3]-[NA-2]-C02H „3+
Ln'J,"-([G-3HNA-2]-Cθ2")3(terpyridine)
R'= [G-3]
Example 18: Preparation of Yb3+- ( [G-4] - [NA-2] -C02 ") 3
(terpyridine) (Reaction Scheme 54)
The title compound was prepared in the same manner as in Example 5 except that [G-4] - [NA-2] -C02H was used instead of [NA-1]-C02H. Also, Er3+- ( [G-4] - [NA-2] -C02 ") 3 (terpyridine) and Nd3+- ( [G-4] - [NA-2] -C02 ~) 3 (terpyridine) were prepared in the same manner.
Yb3+-( [G-4] -[NA-2] -C02 ~) 3 (terpyridine) : λem = 976 n (λex = 325 nm, solid state)
Er3+- ( [G-4] -[NA-2] -C02 ") 3 (terpyridine) : λem = 1530 nm (λex =
325 nm, solid state) Nd3+ -( [G-4] -[NA-2] -C02 ") 3 (terpyridine) : λem = 885, 1054, 1325 nm (λex = 325 nm, solid state) [Reaction Scheme 54]
Figure imgf000061_0001
[G-]-[NA-2]-C02H Ln ,3°+ -([G-4]-[NA-2]-C02-)3(terpyridine)
R' = [G-4]
Example 19: Preparation of Yb3+- ( [G-l] - [NA-3] 2-C02 ") 3 (terpyridine) (Reaction Scheme 55)
The title compound was prepared in the same manner as in Example 5 except that [G-l] - [NA-3] 2-C02H was used instead of [NA- 1]-C02H. Also, Er3+-( [G-l] - [NA-3] 2-C02 ") 3 (terpyridine) and Nd3+- ( [G-l] - [NA-3] 2-C02 ") 3 (terpyridine) were prepared in the same manner.
Yb3+- ( [G-l] - [NA-3] 2-C02 ") 3 (terpyridine) λe = 975 nm (λex = 325 nm, solid state)
Er3+- ( [G-l] - [NA-3] 2-C02 ") 3 (terpyridine) λem = 1532 nm (λe 325 nm, solid state)
Nd3+-( [G-l]- [NA-3] 2-C02 ") 3 (terpyridine) λem = 885, 1053, 1324 nm (λex = 325 nm, solid state) [Reaction Scheme 55]
Figure imgf000061_0002
[G-1]-[NA-3]2-C02H Ln3+-([G-1]-[NA-3]2-C02-)3(terpyridine)
R' = [G-1] Example 20: Preparation of Yb3+- ( [G-2] - [NA-3] 2-C02 ") 3 (terpyridine) (Reaction Scheme 56)
The title compound was prepared in the same manner as in Example 5 except that [G-2] - [NA-3] 2-C02H was used instead of [NA-1]-C02H. Also, Er3+- ( [G-2] - [NA-3] 2-C02 ") 3 ' (terpyridine) and Nd3+-( [G-2] - [NA-3] 2-C02 ~) 3 (terpyridine) were prepared in the same manner.
Yb3+-( [G-2]- [NA-3] 2-C02 ") 3 (terpyridine) : λem = 976 nm (λex = 325 nm, solid state)
Er3+- ([G-2]- [NA-3] 2-C02 ") 3 (terpyridine) : λera = 1532 nm (λex = 325 nm, solid state)
Nd3+- ( [G-2] - [NA-3] 2-CO2 ") 3 (terpyridine) m 16, 1053, 132' nm (λex = 325 nm, solid state)
[Reaction Scheme 56]
Figure imgf000062_0001
[G-2]-[NA-3]2-C02H Ln3+-([G-2]-[NA-3]2-C02-)3(terpyridine)
R' = [G-2]
Example 21; Preparation of YbJ+- ( [G-3] - [NA-3] 2-C02 ") 3 (terpyridine) (Reaction Scheme 57)
The title compound was prepared in the same manner as in Example 5 except that [G-3] - [NA-3] 2-C0H was used instead of [NA-1]-C02H. Also, Er3+- ( [G-3] - [NA-3] 2-C02 ") 3 (terpyridine) and Nd3+- ( [G-3 ] - [NA-3 ] 2-C02 ) 3 (terpyridine) were prepared in the same manner .
Yb3+- ( [G-3 ] - [NA-3 ] 2-C02 ") 3 (terpyridine ) λe = 976 nm (λε 325 nm, solid state )
Er3+- ( [G-3 ] - [NA-3 ] 2-C02 ~) 3 (terpyridine ) λe = 1532 nm (λe 325 nm, solid state )
Nd3+- ( [G-3 ] - [NA-3 ] 2-C02 ") 3 (terpyridine ) λe 886 , 1054 , 1324 nm (λex = 325 nm, solid state) [Reaction Scheme 57 ]
Figure imgf000063_0001
[G-3]-[NA-3]2-C02H Ln3+-([G-3HNA-3]2-C02-)3(terpyridine)
R' = [G-3]
Example 22 Preparation of Yb 3+ ( [G-4]- [NA-3] 2-CO2") 3
(terpyridine) (Reaction Scheme 58) The title compound was prepared in the same manner as in Example 5 except that [G-4] - [NA-3] 2-C02H was used instead of [NA-1]-C02H. Also, Er3+- ( [G-3] - [NA-4] 2-C02 ") 3 (terpyridine) and Nd3+- ( [G-4] - [NA-3] 2-C02 ") 3 (terpyridine) were prepared in the same manner. Yb3+- (.[G-4]- [NA-3] 2-C02 ") 3 (terpyridine) : λem = 976 nm (λex =
325 nm, solid state)
Er3+-( [G-4] -[NA-3] 2-C02 ~) 3 (terpyridine) : λem = 1531 nm (λex =
325 nm, solid state)
Nd3+-( [G-4] -[NA-3] 2-C02 ~) 3 (terpyridine) : λem = 885, 1054, 1324 nm (λex = 325 nm, solid state) [Reaction Scheme 58]
Figure imgf000064_0001
[G-4]-[NA-3]2-C02H Ln3+-([G-4]-[NA-3]2-C02-)3(terpyridine)
R' = [G-4]
. Example 23: Preparation of Yb3+- ( [G-l]- [AN-1] -C02 ") 3
5 (terpyridine) (Reaction Scheme 59)
The title compound was prepared in the same manner as in Example 5 except that [G-l] - [AN-1] -C02H was used instead of [NA-1]-C02H. Also, Er3+- ( [G-l] - [AN-1] -C02 ") 3 (terpyridine) and Nd3+- ( [G-l] - [AN-1] -C02 ") 3 (terpyridine) were prepared in 10. the same manner.
Yb3+- ( [G-l] - [AN-1] -C02 ") 3 (terpyridine) λf = 975 nm (λ€ 442 nm, solid state)
Er3+- ( [G-l] - [AN-1] -C02 ") 3 (terpyridine) λe = 1530 nm (λex = 442' nm, solid state) 15 Nd3+- ( [G-l] - [AN-1] -C02 ~) 3 (terpyridine) λem = 885, 1054, 1325 nm (λex = 442 nm, solid state) [Reaction Scheme 59]
Figure imgf000064_0002
„3+
[G-1]-[AN-1]-C02H LrY3 -([G-1HAN-1]-C02 ")3(terpyridine)
R' = [G-1]
0
Example 24 Preparation of Yb 3J+t- ( [G-l] - [AN-1] -C02 ") 3
(terpyridine) (Reaction Scheme 60) The title compound was prepared in the same manner as in
Example 5 except that [G-2] - [AN-1] -C02H was used instead of [NA-
1]-C02H. Also, Er3+-( [G-2] - [AN-1] -C02 ") 3 (terpyridine) and Nd3+-
( [G-2] - [AN-1] -C02 ") 3 (terpyridine) were prepared in the same manner .
Yb3+- ([G-2]- [AN-1] -C02 ") 3 (terpyridine) : λ6 976 nm (λe 442 nm, solid state)
Er3+- ( [G-2] - [AN-1] -C02 ") 3 (terpyridine) λem = 1530 nm (λex = 442 nm, solid state)
Nd3+-( [G-2] -[AN-1] -C02 ") 3 (terpyridine) : λem = 1054, 1325 nm (λex = 442 nm, solid state)
[Reaction Scheme 60]
Figure imgf000065_0001
[G-2]-[AN-1]-C02H n ,30+t-([G-2]-[AN-1]-CO2-)3(te yridine)
R' = [G-2]
Example 25 Preparation of Yb 3+ - ( [G-3 ] - [AN-1 ] -C02 ") 3
(terpyridine ) (Reaction Scheme 61 )
The title compound was prepared in the same manner as in Example 5 except that [G-3] - [AN-1] -C02H was used instead of [NA- 1 ] -C02H . Also, Er3+- ( [G-3 ] - [AN-1] -C02 ") 3 (terpyridine) and Nd3+- ( [G-3 ] - [AN-1] -CO2 ") 3 (terpyridine ) were prepared in the same manner .
Yb3+- ( [G-3 ] - [AN-1 ] -C02 ~) 3 (terpyridine) λe = 975 nm (λe
442 nm, solid state)
Er3+- ( [G-3] - [AN-1] -C02 ") 3 (terpyridine ) λem = 1531 nm (λe
442 nm, solid state) Nd ]3J++- ( [G-3 ] - [AN-1 ] -C02 ~) 3 (terpyridine) λe 884 , 1052 , 1324 nm (λex = 442 nm, solid state) [Reaction Scheme 61]
Figure imgf000066_0001
[G-3]-[AN-1]-CQ2H Ln ,3°+ -([G-3]-[AN-1]-C02 ')3(terpyridine)
R' = [G-3]
Example 26: Preparation of Yb3+- ( [G-4] - [AN-1] -C02 ") 3 (terpyridine) (Reaction Scheme 62)
The title compound was prepared in the same manner as in Example 5 except that [G-4] - [AN-1] -C02H was used instead of [NA-1]-C02H. Also, Er3+- ( [G-4] - [AN-1] -C02 ") 3 (terpyridine) and Nd3+- ( [G-4] - [AN-1] -C02 ~) 3 (terpyridine) were prepared in the same manner.
Yb3+-( [G-4]- [AN-1] -C02 ~) 3 (terpyridine) : λem = 976 nm (λex = 442 nm, solid state)
Er3+-( [G-4] -[AN-1] -C02 ~) 3 (terpyridine) : λem = 1530 nm (λex = 442 nm, solid state)
Nd3+- ( [G-4] - [AN-1] -C02 ~) 3 (terpyridine) Λem 14, 1052, 1325 nm (λex = 442 nm, solid state) [Reaction Scheme 62]
Figure imgf000066_0002
Figure imgf000066_0003
LnJ+-([G-3]-[AN-1]-C02")3(terpyridine)
R' = [G-4] Example 27: Preparation of Yb3+- ( [G-l] ~ [AN-2] 2-C02_")3 (terpyridine) (Reaction Scheme 63)
The title compound was prepared in the same manner as in Example 5 except that [G-l] - [AN-2] 2-C02H was used instead of [NA- 1]-C02H. Also, Er3+-([G-l]-[AN-2]2-C02 ")3 (terpyridine) and Nd3+- ( [G-l] -[AN-2] 2-C02-) 3 (terpyridine) were prepared in the same manner.
Yb3+- ( [G-l ] - [AN-2 ] 2-CO2 ") 3 (terpyridine) λP = 975 nm (λe 442 nm, solid sta te )
Er3+- ( [G-l ] - [AN- 2 ] 2~C02 ") 3 (terpyridine) λem = 1531 nm (λe
442 nm, solid state)
Nd3+- ( [G-l ] - [AN-2 ] 2-CO2 ") 3 (terpyridine) λem = 884 , 1054 , 1324 nm (λex = 442 nm, solid state) [Reaction Scheme 63 ]
Figure imgf000067_0001
[G-3]-[AN-2]2-C02H nJ+-([G-3]-[AN-2]2-C02-)3(terpyridine)
K- [G-1]
'■Example 28: Preparation of Yb3+- ( [G-2] - [AN-2] 2-C02 ") 3 (terpyridine) (Reaction Scheme 64)
The title compound was prepared in the same manner as in Example 5 except that [G-2] - [AN-2] 2-C02H was used instead of [NA-1]-C02H. Also, Er3+-([G-2]-[AN-2]2-C02 ")3 (terpyridine) and Nd3+-( [G-2] - [AN-2] 2-C02 ")3 (terpyridine) were prepared in the same manner. Yb3+- (' [G-2] - [AN-2] 2-C02 ~) 3 (terpyridine) λem = 975 nm (λe 442 nm, solid state)
Er3+- ( [G-2] - [AN-2] 2-C02 ~) 3 (terpyridine) λem = 1531 nm (λe 442 nm, solid state)
Nd3+- ( [G-2] - [AN-2] 2-C02 ") 3 (terpyridine) λem = 886, 1053, 1325 nm (λex = 442 nm, solid state) [Reaction Scheme 64]
Figure imgf000068_0001
[G-3]-[AN-2]2-C02H Ln3+-([G-3]-[AN-2]2-C02-)3(terpyιϊdine)
K= [G-2]
Example 29: Preparation of Yb3+- ( [G-3] - [AN-2] 2-C02 ") 3 (terpyridine) (Reaction Scheme 65)
The title compound was prepared in the same manner as in Example 5 except that [G-3] - [AN-2] 2-C02H was used instead of [NA- 1]-C02H. Also, Er3+-( [G-3] - [AN-2] 2-C02 ") 3 (terpyridine) and Nd3+- ( [G-3] - [AN-2] 2-C02 ") 3 (terpyridine) were prepared in the same manner.
Yb3+- ( [G-3] - [AN-2] 2-C02 ") 3 (terpyridine) λem = 975 nm (λex = 442 nm, solid state)
Er3+- ( [G-3] - [AN-2] 2-CO2") 3 (terpyridine) λP = 1531 nm (λe 442 nm, solid state)
Nd3+- ( [G-3] - [AN-2] 2-CO2") 3 (terpyridine) λem = 885, 1054, 1325 nm (λex = 442 nm, solid state) [Reaction Scheme 65]
Figure imgf000069_0001
[G-3]-[AN-2]2-C02H Ln3+-([G-3]-[AN-2]2-C02-)3(terpyridine)
R' = [G-3]
Example 30: Preparation of Yb3"1- ( [G-4] - [AN-2] 2-C02 ") 3 (terpyridine) (Reaction Scheme 66)
The title compound was prepared in the same manner as in Example 5 except that [G-4] - [AN-2]2-C02H was used instead of [NA- 1]-C02H. Also, Er3+-( [G-4] -[AN-2] 2-C02 ~) 3 (terpyridine) and Nd3+- ( [G-4]- [AN-2] 2-C02 ~) 3 (terpyridine) were prepared in the same manner.
Yb3+- ( [G-4 ] - [AN-2 ] 2-C02 ") 3 (terpyridine) λP 976 nm (λex = 442 nm, solid state)
Er3+- ( [G-4 ] - [AN-2 ] 2-C02 ") 3 (terpyridine) : λe 1531 nm (λex = 442 nm, solid state)
Nd3+- ( [G-4 ] - [AN-2] 2-C02 ") 3 (terpyridine) λe 14 , 1053, 1324 nm (λex = 442 nm, solid state) [Reaction Scheme 66]
Figure imgf000069_0002
[G-4]-[AN-2]2-C02H Ln3+-([G-4]-[AN-2]2-C02-)3(terpyridine)
R' = [G-4]
Example 31: Preparation of Yb3+- [porphyrin (phenyl) 3 (COO )] 3 (Reaction Scheme 67) The title compound was prepared in the same manner as in Example 1, using 5, 10, 15-triphenyl-20- (4-carboxyphenyl) porphyrin. Also, Er3+- [porphyrin (phenyl) 3 (COO") ] 3 and Nd3+-
[porphyrin (phenyl) 3 (COO") ]3 were prepared in the same manner. FT-IR (KBr, cm"1) : 3316, 1596, 1402. Yb3+- [porphyrin (phenyl) 3 (COO") ] 3 λem = 975 nm (λex = 442 nm, solid state)
Er3+- [porphyrin (phenyl) 3 (COO") ] 3 λe = 1455 nm (λex = 442 nm, solid state)
Nd3+- [porphyrin (phenyl) 3 (COO") ] 3 λem = 885, 1054, 1323 nm (λe 442 nm, solid state)
[Reaction Scheme 67]
Figure imgf000070_0001
Example 32: Preparation of Yb3+- [porphyrin (phenyl) 3 (COO" ) zinc] 3 (Reaction Scheme 68)
The title compound was prepared in the same manner as in Example 1 except that [5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zince was used instead of 5,10,15- triphenyl-20- (4-carboxyphenyl) porphyrin. Also, Er3+-
[porphyrin (phenyl) 3 (COO") zinc]3 and Nd3+- [porphyrin (phenyl) 3 (COO" ) zinc] 3 were prepared in the same manner. FT-IR (KBr, cm"1) : 1596, 1410
Yb3+- [porphyrin (phenyl) 3 (COO") zinc] 3 : λem = 975 nm (λex = 442 nm, solid state) Er3+- [porphyrin (phenyl) 3 (COO") zinc] 3 λ„ 1520 nm (λe 442 nm, solid state)
Nd3+- [porphyrin (phenyl) 3 (C00~) zinc] 3 λe 15, 1054, 1323 nm (λex = 442 nm, solid state)
Example 33: Preparation of Yb3+- [porphyrin (phenyl) 3 (COO" ) platinum] 3 (Reaction Scheme 68)
The title compound was prepared in the same manner as in
Example 1 except that [5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum was used instead of 5,10,15- triphenyl-20- (4-carboxyphenyl) porphyrin. Also, Er3+-
[porphyrin (phenyl) 3 (COO") platinum] 3 and Nd3+-
[porphyrin (phenyl) 3 (COO") platinum] 3 were prepared in 'the same manner. FT-IR (KBr, cm-1) : 1599, 1417.
Yb3+- [porphyrin (phenyl) 3 (C00~) platinum] 3 :λem =975 nm (λex = 442 nm, solid state)
Er3+- [porphyrin (phenyl) 3 (C00~) platinum] 3 :λem =1520 nm (λex = 442 nm, solid state) Nd3+- [porphyrin (phenyl) 3 (COO~) platinum] 3 : λem = 885, 1054, 1323 nm (λex = 442 nm, solid state) [Reaction Scheme 68]
Figure imgf000071_0001
M is Zn or Pt Example 34: Preparation of Yb3+- [porphyrin (phenyl) 3 (COO~_ ) ]3 (bipyridine) (Reaction Scheme 69)
The title compound was prepared in the same manner as in Example 3, using 5, 10, 15-triphenyl-20- (4-carboxyphenyl) porphyrin, with the addition of anhydrous YbCl3 and bipyridine. Also, Er3+- [porphyrin (phenyl) 3 (COO") ] 3 (bipyridine) and Nd3+-
[porphyrin (phenyl) 3 (C0O~) ] 3 (bipyridine) were prepared in the same manner.
FT-IR (KBr, cm"1) : 3310, 1599, 1400. Yb3+- [porphyrin (phenyl) 3 (COO") ] 3 (bipyridine) : λ6 = 975 nm (λe 442 nm, solid state)
Er3+- [porphyrin (phenyl) - (COO") ] 3 (bipyridine) : λP =1520nm (λe =442 nm, solid state)
Nd3+- [porphyrin (phenyl) 3 (COO") ] 3 (bipyridine) λ<= = 885, 1054, 1323 nm (λex = 442 nm, solid state)
[Reaction Scheme 69]
Figure imgf000072_0001
Example 35: Preparation of Yb3+- [porphyrin (phenyl) 3 (COO"
) zinc] 3 (bipyridine) (Reaction Scheme 70)
The title compound was prepared in the same manner as in
Example 3 except that [5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc was used instead of 5,10,15- triphenyl-20- (4-carboxyphenyl) porphyrin. Also, Er3+-
[porphyrin (phenyl) 3 (COO") zinc] 3 (bipyridine) and Nd3+- [porphyrin (phenyl ) 3 (COO") zinc] 3 (bipyridine ) were prepared in the same manner .
FT-IR (KBr, cm"1) : 1600, 1401.
Yb3+- [porphyrin (phenyl) 3 (COO") zinc] 3 (bipyridine) : λem =978 nm (λex
= 442 nm, solid state)
Er3+- [porphyrin (phenyl) 3 (COO") zinc] 3 (bipyridine) : λem =1522nm (λex
= 442 nm, solid state)
Nd3+- [porphyrin (phenyl) 3 (COO") zinc] 3 (bipyridine) : λem = 890, 1052,
1323 nm (λex = 442 nm, solid state)
Example 36: Preparation of Yb3"1"- [porphyrin (phenyl) 3 (COO"
) platinum] 3 (bipyridine) (Reaction Scheme 70)
The title compound was prepared in the same manner as in
Example 3 except that [5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum was used instead of 5,10,15- triphenyl-20- (4-carboxyphenyl) porphyrin. Also, Er3+-
[porphyrin (phenyl) 3 (C00~) platinum] 3 (bipyridine) and Nd3+-
[porphyrin (phenyl) 3 (COO~) platinum] 3 (bipyridine) were prepared in the same manner. FT-IR (KBr, cm"1) : 1599, 1410.
Yb3+- [porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) :λera =978nm(λex
=442 nm, solid state)
Er3+- [porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) :λem =1524nm
(λex=442nm, solid state) Nd3+- [porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) : λem = 890,
1052, 1323 nm (λex = 442 nm, solid state) [Reaction Scheme 70]
Figure imgf000074_0001
M is Zn or Pt
Example 37: Preparation of Yb3+- [porphyrin (phenyl) 3 (COO~ )] 3 (terpyridine) (Reaction Scheme 71)
The title compound was prepared in the same manner as in Example 3 except that terpyridine was used instead of bipyridine.
Also,' Er - [porphyrin (phenyl) 3 (COO )] 3 (terpyridine) and Nd3+-
[porphyrin (phenyl) 3 (COO )] 3 (terpyridine) were prepared in the same manner.
FT-IR (KBr, cm"1) : 3314, 1604, 1405.
Yb3+- [porphyrin (phenyl) 3 (COO") ] 3 (terpyridine) :λem =978nm (λex =442 nm, solid state)
Er3+- [porphyrin (phenyl) 3 (COO") ] 3 (terpyridine) : λem =1428nm (λex =442nm, solid state)
Nd3+- [porphyrin (phenyl) 3 (C0O~) ] 3 (terpyridine) : λem = 890, 1052, 1323 nm (λex = 442 nm, solid state) [Reaction Scheme 71]
Figure imgf000074_0002
Example 38: Preparation of Yb3"1"- [porphyrin (phenyl) 3(COO~ ) zinc] 3 (terpyridine) (Reaction Scheme 72)
The title compound was prepared in the same manner as in Example 3 except that [5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc was used instead of [5,10,15- triphenyl-20- (4-carboxyphenyl) porphyrin. Also, Er3+-'
[porphyrin (phenyl) 3 (COO") zinc] 3 (terpyridine) and Nd3+- [porphyrin (phenyl) 3 (COO") zinc] 3 (terpyridine) were prepared in the same manner.
FT-IR (KBr, cm"1) : 1600, 1402.
Yb3+- [porphyrin (phenyl) 3 (C00~) zinc] 3 (terpyridine) :λem = 978 nm (λex = 442 nm, solid state) Er3+- [porphyrin (phenyl) 3 (COO") zinc] 3 (terpyridine) : λe = 1520 nm (λex = 442 nm, solid state)
Nd3+- [porphyrin (phenyl) 3 (COO") zinc] 3 (terpyridine) : λem = 890, 1052, 1323 nm (λex = 442 nm, solid state)
Example 39: Preparation of Yb3+- [porphyrin (phenyl) 3 (COO~ ) platinum] 3 (terpyridine) (Reaction Scheme 72)
The title compound was prepared in the same manner as in
Example 3 except that ( [5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum) was used instead of [5,10,15- triphenyl-20- (4-carboxyphenyl) porphyrin. • Also, Er3+- [porphyrin (phenyl) 3 (COO") platinum] 3 (terpyridine) and Nd3+-
[porphyrin (phenyl) 3 (COO") platinum] 3 (terpyridine) . were prepared in the same manner.
FT-IR (KBr, cm"1) : 1598, 1408.
Yb3+- [porphyrin (phenyl) 3 (C00~) platinum] 3 (terpyridine) : λem = 978 nm (λex = 442 nm, solid state) Er-3+- [porphyrin (phenyl) 3 (COO") platinum] 3 (terpyridine) λP 1524 nm (λex = 442 nm, solid state)
Nd -[porphyrin (phenyl) 3 (COO") platinum] 3(terpyridine) : λem = 890, 1052, 1323 nm (λex = 442 nm, solid state) [Reaction Scheme 72]
Figure imgf000076_0001
M is Zn or Pt
Example 40 : Preparation of Yb 3+ [[6-l]3- porphyrin (phenyl) 3 (COO") ]3 (Reaction Scheme 73)
The title compound was prepared in the same manner as in Example 1, using [G-l] 3-5, 10, 15-triphenyl-20- (4- carboxymethyl) porphyrin. Also, Er3+- [ [G-l] 3- porphyrin (phenyl) 3 (COO") ]3 and Nd3+- [ [G-l] 3- porphyrin (phenyl) 3 (COO~) ] 3 were prepared in the same manner. Yb3+-[ [G-l] 3-porphyrin (phenyl) 3 (COO") ]3 : λem = 975 nm (λex = 442 nm, solid state)
Er3+- [ [G-l] 3-porphyrin (phenyl) 3 (COO") ] 3 λem = 1455 nm (λex = 442 nm, solid state)
NdJ+- [ [G-l] 3-porphyrin (phenyl) 3 (COO") ] 3 A -m 15 , 1054 , 1323 nm (λex = 442 nm, solid state)
Example 41 : Preparation of .3+
Yb^-[[G-2] 3- porphyrin (phenyl) 3 (COO )]3 (Reaction Scheme 73) The title compound was prepared in the same manner as in
Example 1, using [G-2]3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin. Also, Er3+- [ [G-2] 3- porphyrin (phenyl) 3(COO") ]3 and Nd3+- [ [G-2] 3-porphyrin (phenyl) 3 (COO" )]3 were prepared in the same manner.
Yb3+-[ [G-2] 3-porphyrin (phenyl) 3 (COO~) ] 3 : λem = 975 nm (λex = 442 nm, solid state)
Er3+- [[G-2] 3-porphyrin (phenyl) 3 (C00~) ] 3 : λem = 1455 nm (λex = 442 nm, solid state) Nd3+- [[G-2] 3-porphyrin (phenyl) 3 (C00~) ] 3 : λem = 885, 1054, 1323 nm (λex = 442 nm, solid state)
Example 42j Preparation of Yb3+- [ [G-3]3- porphyrin (phenyl) 3 (COO") ]3_ (Reaction Scheme 73) The title compound was prepared in the same manner as in
Example 1, using [G-3] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin. Also, Er3+- [ [G-3] 3- porphyrin (phenyl) 3 (COO") ] 3 and Nd3+- [ [G-3] 3-porphyrin (phenyl) 3 (COO"
)]3 were prepared in the same manner. Yb3+-[ [G-3] 3-porphyrin (phenyl) 3 (COO") ] 3 : λem - 975 nm (λex = 442 nm, solid state)
Er3+- [ [G-3 ] 3-porphyrin (phenyl ) 3 (COO") ] 3 : λem = 1455 nm (λex = 442 nm, solid state)
Nd3+-[ [G-3] 3-porphyrin (phenyl) 3 (COO") ] 3 : λem = 885, 1054, 1323 nm (λex = 442 nm, solid state)
Example 4_3j Preparation of ■ Yb3+- [ [G-4] 3- porphyrin (phenyl) 3 (COO") ]3 (Reaction Scheme 73)
The title compound was prepared in the same manner as in Example 1, using [G-4]3~5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin. Also, Er+-[[G-4]3- porphyrin (phenyl) 3 (COO") ]3 and Nd3+- [ [G-4] 3-porphyrin (phenyl) 3 (COO" )]3 were prepared in the same manner. Yb3+-[ [G-4] 3-porphyrin (phenyl) 3 (COO") ]3 λem - 975 nm (λex = 442 nm, solid state)
Er3+- [ [G-4] 3-porphyrin (phenyl) 3 (COO~) ] 3 λP 1455 nm (λex = 442 nm, solid state)
Nd3+- [ [G-4 ] 3-porphyrin (phenyl) 3 (C00~) '] 3 Apm — 185, 1054, 1323 nm (λex = 442 nm, solid state) [Reaction Scheme 73]
Figure imgf000078_0001
Figure imgf000078_0002
porphyrin (phenyl) 3 (COO") zinc] 3 (Reaction Scheme 74)'
The title compound was prepared in the same manner as in Example 1, using [ [G-l] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zince. Also,
Figure imgf000078_0003
porphyrin (phenyl) 3 (COO") zinc] 3 and Nd 3-3+"*"- [ [G-l] 3- porphyrin (phenyl) 3 (COO~) zinc] 3 were prepared in the same manner.
Yb3+- [ [G-l] 3-porphyrin (phenyl) 3 (COO~) zinc] 3 em = 975 nm (λex =
442 nm, solid state)
Er3+- [ [G-l] 3-porphyrin (phenyl) 3 (COO") zinc] 3 λem = 1520 nm (λex =
442 nm, solid state)
Nd3+- [ [G-l] 3-porphyrin (phenyl) 3 (COO") zinc] 3 λem = 885, 1054, 1323 nm (λex = 442 nm, solid state) Example 4_5 Preparation of Yb3+- [ [G-2]3- porphyrin (phenyl) 3 (COO") zinc] 3 (Reaction Scheme 74)
The title compound was prepared in the same manner as in Example- 1, using [ [G-2] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er3+- [ [G-2] 3- porphyrin (phenyl) 3 (COO") zinc] 3 and Nd3+- [ [G-2] 3- porphyrin (phenyl) 3 (COO~) zinc] 3 were prepared in the same manner. Yb3+- [ [G-2] 3-porphyrin (phenyl) 3 (COO") zinc] 3 : λem = 975 nm (λex = 442 nm, solid state) Er3+-[ [G-2] 3-porphyrin (phenyl) 3 (COO") zinc]3 : λem = 1520 nm (λex = 442 nm, solid state)
Nd3+-[ [G-2] 3-porphyrin (phenyl) 3 (COO") zinc] 3 : λem = 885, 1054, 1323 nm (λex = 442 nm, solid state)
Example 4_6 Preparation of Yb3+- [ [G-3]3- porphyrin (phenyl) 3 (COO") zinc] 3 (Reaction Scheme 74)
The title compound was prepared in the same manner as in
Example 1, using [ [G-3] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er3+- [ [G-3] 3- porphyrin (phenyl) 3 (COO") zinc] 3 and Nd3+- [ [G-3] 3- porphyrin (phenyl) 3 (C00~) zinc]3 were prepared in the same manner.
Yb3+- [[G-3] 3-porphyrin (phenyl) 3 (COO") zinc] 3 : λem = 975 nm (λex =
442 nm, solid state)
Er3+- [ [G-3] 3-porphyrin (phenyl)-3 (COO") zinc] 3 : λem = 1520 nm (λex =. 442 nm, solid state)
Nd3+-[ [G-3] 3-porphyrin (phenyl) 3 (COO") zinc] 3 : λem = 885, 1054, 1323 nm (λex = 442 nm, solid state)
Example 47j Preparation of Yb3+- [ [G-4]3- porphyrin (phenyl) 3 (COO") zinc] 3 (Reaction Scheme 74) The title compound was prepared in the same manner as in Example 1, using [ [G-4] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er3+- [ [G-4] 3- porphyrin (phenyl) 3 (C00~) zinc] 3 and Nd3+- [ [G-4] 3- porphyrin (phenyl) 3 (COO") zinc] 3 were prepared in the same amnner. Yb3+-[ [G-4] 3-porphyrin (phenyl) 3(COO~) zinc] 3 : λem = 975 nm (λex = 442 nm, solid state)
Er3+-[ [G-4] 3-porphyrin (phenyl) 3 (COO~) zinc] 3 : λem = 1520 nm (λex = 442 nm, solid state) Nd3+-[ [G-4] 3-porphyrin (phenyl) 3 (COO") zinc] 3 : λem = 885, 1054, 1323 nm (λex = 442 nm, solid state)
Example 48j Preparation of Yb3+- [ [G-l]3- porphyrin (phenyl) 3 (C00~) platinum] 3 (Reaction Scheme 74) The title compound was prepared in the same manner as in Example 1, using [ [G-l] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] latinum. Also, Er3+- [ [G-l] 3- porphyrin (phenyl) 3 (COO") platinum] 3 and Nd3+- [ [G-l] 3- porphyrin (phenyl) 3 (COO") platinum] 3 were prepared in the same manner.
Yb3+- [ [G-l] 3-porphyrin (phenyl) 3 (COO~) platinum] 3 : λem = 975 nm (λex = 442 nm, solid state)
Er3+- [ [G-l] 3-porphyrin (phenyl) 3 (C00~) platinum] 3 : λem = 1520 nm (λex = 442 nm, solid state) Nd3+-[ [G-l] 3-porphyrin (phenyl) 3 (COO~) platinum] 3 : λem = 885, 1054, 1323 nm (λex = 442 nm, solid state)
Example 49j Preparation of Yb3+- [ [G-2]3- porphyrin (phenyl) 3 (COO") platinum] 3 (Reaction Scheme 74) The title compound was prepared in the same manner as in Example 1, using [ [G-2] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum. Also, Er3+- [ [G-2]3- porphyrin (phenyl) 3 (COO~) platinum] 3 and Nd3+- [ [G-2] 3- porphyrin (phenyl) 3 (COO~) platinum] 3 were prepared in the same manner .
Yb +-[ [G-2] 3-porphyrin (phenyl) j (COO") platinum] 3 : λem = 975 nm (λex
- 442 nm, solid state)
Er +-[ [G-2] 3-porphyrin (phenyl) 3 (COO") platinum] 3 : λem = 1520 nm (λex
= 442 nm, solid state)
Nd3+-[ [G-2] 3-porphyrin (phenyl) 3 (COO") platinum] 3 : λem = 885, 1054,
1323 nm (λex = 442 nm, solid state)
Example 50j_ Preparation of Yb3+- [ [G-3]3-
£orphyrin (phenyl) 3 (CC-O") platinum]3 (Reaction Scheme 74)'
The title compound was prepared in the same manner as in Example 1, using [G-3]3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum. Also, Er3+- [ [G-3] 3- porphyrin (phenyl) 3 (COO") platinum] 3 and Nd3+- [ [G-3] 3- porphyrin (phenyl) 3 (COO") platinum] 3 were prepared in the same manner. Yb3+- [ [G-3] 3-υorphyrin (phenyl) 3 (COO~) platinum] 3 : λem = 975 nm (λex = 442 nm, solid state)
Er3+- [ [G-3J 3-porphyrin (phenyl) 3 (COO") platinum] 3 : λem = 1520 nm (λex = 442 Tii'i, solid state) M3+-' [G-3] 3-porphyrin (phenyl) 3 (COO") platinum] 3 : λem = 885, 1054, 1323 nrα (λex = 442 nm, solid state)
Example . 51: Preparation of Yb3+- [ [G-4]3- porphyrin (phenyl) 3 (COO") platinum] 3_ (Reaction Scheme 74)
The title compound was prepared in the same manner as in Example 1, using [ [G-4] 3-5, 10, 15-triρhenyl-20- (4- ca'rboxyphenyl) porphyrin] platinum. Also, Er3+- [ [G-4] 3- porphyrin (phenyl) 3 (COO ) platinum] 3 and
Figure imgf000082_0001
porphyrin (phenyl) 3 (COO") platinum] 3 were prepared in the same manner
Yb .3+ - [L[G-4 ] 3-porphyriinn (phenyl) 3 (COO") platinum] 3 λem = 975 nm (λe
= 442 ήm, so l:id sta_.t_e.),
Er3+- [ [G-4]3-porphyrin (phenyl) 3 (COO") platinum] 3 λem = 1520 nm (λe
= 442 nm, solid state)
Nd3+-'[ [G-4] 3-porphyrin (phenyl) 3 (COO") platinum] 3 λem = 885 , 1054 ,
1323 nm (λex = 442 nm, solid state)
[Reaction Scheme 74]
Figure imgf000082_0002
Example 52 : Preparation of Yb 3+ [[G-l]3- porphyrin (phenyl) 3 (COO") ] 3 (bipyridine) (Reaction Scheme 75)
The title compound was prepared in the same manner as in Example 3, using [G-l] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin with the addition of anhydrous YbCl3 and bipyridine. Also, Er3+- [ [G-l] 3-porphyrin (phenyl) 3 (COO"
) ]3 (bipyridine) and Nd3+- [ [G-l] 3-Porphyrin (phenyl) 3 (COO" )] 3 (bipyridine) were prepared in the same manner. Yb3+- [ [G-l] 3-porphyrin (phenyl) 3 (COO") ] 3 (bipyridine) e = 975 nm (λex = 442 nm, solid state)
Er3+- [ [G-l] 3-porphyrin (phenyl) 3 (COO") ] 3 (bipyridine) λem = 1520 nm (λex = 442 nm, solid state) Nd3+-[ [G-l] 3-porphyrin (phenyl) 3 (COO ) ]3 (bipyridine) : λem = 885, 1054, 1323 nm (λex = 442 nm, solid state)
Example 53 Preparation of Yb34"- [ [G-2]3- porphyrin (phenyl) 3 (COO") ] 3 (bipyridine) (Reaction Scheme 75)
The title compound was prepared in the same manner as in Example 3, using [G-2] 3-5, 10, 15-Triphenyl-20- (4- carboxyphenyl) porphyrin with the addition of anhydrous YbCl3 and bipyridine. Also, Er3+- [ [G-2] 3-porphyrin (phenyl) 3 (COO~ )] 3 (bipyridine) and Nd3+- [ [G-2] 3-porphyrin (phenyl) 3 (COO" )] 3 (bipyridine) were prepared in the same manner.
Yb3+- [ [G-2] 3-porphyrin (phenyl) 3 (COO~) ] 3 (bipyridine) : λem = 975 nm (λex = 442 nm, solid state)
Er3+- [ [G-2] 3-porphyrin (phenyl) 3 (COO~) ] 3 (bipyridine) : λe - 1520 nm (λex = 442 nm, solid state)
Nd3+- [ [G-2] 3-porphyrin (phenyl) 3 (COO") ] 3 (bipyridine) : λem = 885, 1054, 1323 nm (λex = 442 nm, solid state)
Example 5_4j Preparation of Yb3+- [ [G-3] 3- porphyrin (phenyl) 3 (COO") ] 3 (bipyridine) (Reaction Scheme 75)
■ The title compound was prepared in the same manner as in
Example 3, using [G-3] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin with the addition of anhydrous YbCl3 and bipyridine.- Also, Er3+- [ [G-3] 3-porphyrin (phenyl) 3 (COO" ) ] 3 (bipyridine) and Nd3+- [ [G-3] 3-porphyrin (phenyl) 3 (COO"
)] 3 (bipyridine) were prepared in the same manner.
Yb3+-[ [G-3] 3-porphyrin (phenyl) 3 (COO") ] 3 (bipyridine) : λem = 975 nm
(λex = 442 nm, solid state)
Er3+-[ [G-3] 3-porphyrin (phenyl) 3 (COO") ] 3 (bipyridine) : λem = 1520 nm (λex = 442 nm, solid state) Nd ]3+-[ [G-3] 3-porphyrin (phenyl) 3 (COO") ] 3 (bipyridine) λe = 885, 1054, 1323 nm (λex = 442 nm, solid state)
Example 55: Preparation of Yb .3J+'-[[G-4]3- porphyrin (phenyl) 3 (COO") ] 3 (bipyridine) (Reaction Scheme 75)
The title compound was prepared in the same manner as in Example 3, using [G-4]3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin with the addition of anhydrous YbCl3 and bipyridine. Also, Er3+- [ [G-4] 3-porphyrin (phenyl) 3 (COO~
) ]3 (bipyridine) and Nd3+- [ [G-4] 3-porphyrin (phenyl) 3 (COO"
)] 3 (bipyridine) were prepared in the same manner. Yb3+- [ [G-4] 3-porphyrin (phenyl) 3 (COO") ] 3 (bipyridine) : λe = 975 nm (λex = 442 nm, solid state)
Er3+- [ [G-4] 3-porphyrin (phenyl) 3 (COO") ] 3 (bipyridine) : λer 1520 nm (λex = 442 nm, solid state)
Nd3+- [ [G-4] 3-porphyrin (phenyl) 3 (COO") ]3 (bipyridine) λe = 885, 1054, 1323 nm (λex = 442 nm, solid state) [Reaction Scheme 75]
Figure imgf000084_0001
Figure imgf000084_0002
porphyrin (phenyl) 3 (COO") zinc] 3 (bipyridine) (Reaction Scheme 76) The title compound was prepared in the same manner as in Example 3, using [ [G-l] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl ) porphyrin] zinc . Also, Er3+- [ [G-l] 3- porphyrin (phenyl ) 3 (C00~) zinc] 3 (bipyridine ) and Nd3+- [ [G-l] 3- porphyrin (phenyl ) 3 (COO") zinc] 3 (bipyridine ) were prepared in the same manner . Yb3+- [ [G-l ] 3-porphyrin (phenyl ) 3 (COO") zinc] 3 (bipyridine ) : λem = 978 nm (λex = 442 nm, solid state ) E Err33++-- [[ [[GG--ll]] 33--ppoorrpphhyyrriinn ((pphheennyyl) 3 (COO ) zinc] 3 (bipyridine ) : λem =1522 nm (λex =442 nm, solid state N Ndd33++-- [[ [[GG--ll ]] 33--ppoorrpphhyyrriinn ((pphheennyy!l ) 3 (COO") zinc] 3 (bipyridine ) : λem =890 , 1052 , 1323 nm (λex =442 nm, solid state
Example 57_: Preparation of Yb3+-_ [ [G-2]3- porphyrin (phenyl) 3 (COO") zinc] 3 (bipyridine) (Reaction Scheme 76)
The title compound was prepared in the same manner as in Example 3, using [ [G-2] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er3+- [ [G-2]3- porphyrin (phenyl) 3 (COO") zinc] 3 (bipyridine) and Nd3+- [ [G-2] 3- porphyrin (phenyl) 3 (COO~) zinc] 3 (bipyridine) were synthesized in the same manner. Yb3+- [ [G-2] 3-porphyrin (phenyl) 3 (COO") zinc] 3 (bipyridine) : λem = 978 nm (λex = 442 nm, solid state)
Er3+- [ [G-2] 3-porphyrin (phenyl) 3 (COO") zinc] 3 (bipyridine) : λem 1522 nm (λex = 442 nm, solid state) Nd3+- [ [G-2] 3-porphyrin (-phenyl) 3 (COO") zinc] 3 (bipyridine) : λem- = 890, 1052, 1323 nm (λex = 442 nm, solid state)
• Example 58 Preparation of Yb3+- [ [G-3]3_- porphyrin (phenyl) 3 (COO") zinc] 3 (bipyridine) (Reaction Scheme 76)
The title compound was prepared in the same manner as Example 3, using [ [G-3] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl)porphypin] zinc. Also, Er3+- [ [G-3] 3- porphyrin (phenyl) 3 (COO") zinc] 3 (bipyridine) and Nd3+- [ [G-3] 3- porphyrin (phenyl) 3 (COO") zinc] 3 (bipyridine) were synthesized in the same manner. Yb3+-[ [G-3] 3-porphyrin (phenyl) 3 (C00~) zinc] 3 (bipyridine) : λem = 978 nm (λex = 442 nm, solid state) E Err33++-- [[ [[GG--33]] 33--ppoorrpphhyyrriinn ((pphheennyyll)) 3 (COO ) zinc] 3 (bipyridine) : λe 1522 nm (λex = 442 nm, solid state) N Ndd33++-- [[ [[GG--33]] 33--ppoorrpphhyyrriinn ((pphheennyyll)) 33 ((CCOOOO") zinc] 3 (bipyridine) : λem = 890, 1052, 1323 nm (λex = 442 nm, solid state)
Example 59j Preparation ■ of Yb - [ [G-4]3- porphyrin (phenyl) 3 (COO") zinc] 3 (bipyridine) (Reaction Scheme 76)
The title compound was prepared in the same manner as in
Example, using [ [G-4] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er3+- [ [G-4] 3- porphyrin (phenyl) 3 (COO") zinc] 3 (bipyridine) and Nd3+- [ [G-4] 3- porphyrin (phenyl) 3 (COO") zinc] 3 (bipyridine) were prepared in the same manner.
Yb3+- [ [G-4 ] 3-porphyrin (phenyl) 3 (COO") zinc] 3 (bipyridine) : λem = 978 nm (λex = 442 nm, solid state)
Er3+- [ [G-4 ] 3-porphyrin (phenyl ) 3 (COO") zinc] 3 (bipyridine ) : λem =
1522 nm (λex = 442 nm, solid state )
Nd3+- [ [G-4 ] 3-porphyrin (phenyl ) 3 (COO") zinc] 3 (bipyridine) : λem = 890 ,
1052 , 1323 nm (λex = 442 nm, solid state )
Example 60 Preparation of Yb3+- [ [G-l ] 3- porphyrin (phenyl ) 3 (COO") platinum] 3 (bipyridine ) (Reaction Scheme
76)
The title compound was prepared in the same manner as in Example 3, using [ [G-l]3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum. Also, Er3+- [ [G-l] 3- porphyrin (phenyl) 3 (COO ) platinum] 3 (bipyridine) and Nd3+- [ [G-l] 3- porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) were prepared in the same manner.
Yb • -[ [G-l]3-porphyrin(phenyl)3(COO")platinum]3(bipyridine) : λem = 978 nm (λex = 442 nm, solid state)
Er3+-[ [G-l] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) : λem = 1524 nm (λex = 442 nm, solid state)
Nd3+-[- [G-l] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) : λem = 890, 1052, 1323 nm (Λex = 442 nm, solid state)
Example 6 Preparation of Yb3+- [ [G-2]3- porphyrin (phenyl) 3 (COO") platinum] 3_ (bipyridine) (Reaction Scheme
76)
The t tle compound was prepared in the same manner as in Example 3, using [ [G-2]3~5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum. Also, Er3+- [ [G-2] 3- porphyrin (phenyl) 3 (COO~) platinum] 3 (bipyridine) and Nd3+- [ [G-2] 3- poryhyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) were prepared in the same manner. Yb3+- [ [G-2] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) : λem =
978 nm (λex = 442 nm, solid state)
Er3+- [ [G-2] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) : λem =
1524 nm (λex = 442 nm, solid state)
Nd3+- [ [G-2] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) : λem = 890, 1052, 1323 nm (λex = 442 nm, solid state)
Example 62 Preparation of Yb3+- [ [G-3]3- porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) (Reaction Scheme 76) The title compound was prepared in the same manner as in Example 3, using [ [G-3] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum. Also, in the same manner,
Er3+-[ [G-3] 3-porphyrin (phenyl) 3 (COO~) platinum] 3 (bipyridine) and
Nd3+- [ [G-3] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) were prepared.
Yb3+-[ [G-3] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) : λem =
978 nm (λex = 442' nm, solid state)
Er3+- [ [G-3]3-porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) •Λ.em
1524 nm (λex = 442 nm, solid state)
Nd3+- [ [G-3] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) : λem =
890, 1052, 1323 nm (λex = 442 nm, solid state)
Example 63j Preparation of Yb34"- [ [G-4] 3- porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) (Reaction Scheme 76) The title compound was prepared in the same manner as in
Example 3, using [ [G-4] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum. Also, Er3+- [ [G-4] 3- porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) and Nd3+- [ [G-4] 3- porphyrin (phenyl) 3 (COO~) platinum] 3 (bipyridine) were synthesized in the same manner.
Yb3+- [ [G-4] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) : λem = 978 nm (λex = 442 nm, solid state)
Er3+- [ [G-4] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) : λem = 1524 nm (λex = 442 nm, solid state) Nd3+- [ [G-4] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (bipyridine) : λem = 890, 1052, 1323 nm (λex = 442 nm, solid state) [Reaction Scheme 76]
Figure imgf000089_0001
Figure imgf000089_0002
porphyrin (phenyl) 3 (COO~) ]3 (terpyridine) (Reaction Scheme 77)
The title compound was prepared in the same manner as in Example 3 except that terpyridine was used instead of bipyridine. Also, Er3+- [ [G-l] 3-porphyrin (phenyl) 3 (COO") ] 3 (terpyridine) and Nd3+- [ [G-l] 3-porphyrin (phenyl) 3 (C00~) ] 3 (terpyridine) were prepared in the same manner.
Yb3+- [ [G-l] 3-porphyrin (phenyl) 3 (COO") ] 3 (terpyridine) :λem=978 nm (λex = 442 nm, solid state)
Er3+- [ [G-l] 3-porphyrin (phenyl) 3 (COO") ] 3 (terpyridine) :λem =1428 nm (λex = 442 nm, solid state)
Nd3+-[ [G-l] 3-porphyrin (phenyl) 3 (COO") ] 3 (terpyridine) : λeιt=890, 1052,1323 nm(λex=442nm, solid state)
Example 65: Preparation of Yb .3J+"-[[G-2]3- porphyrin (phenyl) 3 (COO") ] 3 (terpyridine) (Reaction Scheme 77)
The title compound was prepared in the same manner as in Example 3 except that terpyridine was used instead of bipyridine. Also, Er3+- [ [G-2] 3-porphyrin (phenyl) 3 (COO") ] 3 (terpyridine) and
Nd -[ [G-2] 3-porphyrin (phenyl) 3 (COO ) ] 3 (terpyridine) were synthesized in the same manner .
Yb3+- [ [G-2 ] 3-porphyrin (phenyl) 3 (C00~) ] 3 (terpyridine ) : λern=978nm (λex
= 442 nm, solid state) Er3+-[ [G-2] 3-porphyrin (phenyl) 3 (COO )] 3 (terpyridine) :λΘm =1428nm
(λex =442 nm, solid state) N Ndd33++-- [[ [[GG--22 ]] 33--ppoorrpphhyyrriinn ((pphheernyl) 3 (COO )] 3 (terpyridine) :λem =890, 1052, 1323nm (λex=442 nm, solid state)
Example 66_: Preparation of Yb3"1"- [ [G-3]3- porphyri (phenyl) 3 (COO") ] 3 (terpyridine) (Reaction Scheme 77)
The title compound was prepared in the same manner as in
Example 3 except that terpyridine was used bipyridine. Also, Er3+-[ [G-3] 3-porphyrin (phenyl) 3 (COO") ] 3 (terpyridine) and Nd3+-[[G-
3] 3-porphyrin (phenyl) 3 (COO~) ] 3 (terpyridine) were prepared in the same manner.
Yb3+- [ [G-3] 3-porphyrin (phenyl) 3 (COO") ] 3 (terpyridine) : λem =978nm
(λex= 442 nm, solid state) Er3+-[ [G-3] 3-porphyrin (phenyl) 3 (COO") ] 3 (terpyridine) :λem =1428nm
(λex = 442 nm, solid state)
Nd3+-[ [G-3] 3-porphyrin (phenyl) 3 (COO") ] 3 (terpyridine) :λem= 890, 1052,
1323nm (λex = 442 nm, solid state)
Example 67_: Preparation of Yb3+- [ [G-4]3_- porphyrin (phenyl) 3 (COO~) ] 3 (terpyridine) (Reaction Scheme 77)
The title compound was prepared in the same manner as in
Example 3 except that terpyridine was used instead of bipyridine.
Also, Er3+- [ [G-4] 3-porphyrin (phenyl) 3 (COO") ] 3 (terpyridine) and Nd3+- [ [G-4] 3-porphyrin (phenyl) 3 (COO") ] 3 (terpyridine) were prepared in the same manner.
Yb3+- [ [G-4 ] 3-porphyrin (phenyl) 3 (COO") ] 3 (terpyridine ) : λem =978nm (λex
= 442 nm, solid state)
Er3+- [ [G-4 ] 3-porphyrin (phenyl ) 3 (COO") ] 3 (terpyridine ) : λem =1428nm (λex = 442 nm, solid state ) Nd j3J+.-[ [G-4] 3-porphyrin (phenyl) 3 (COO") ]3 (terpyridine) : λem=890, 1052, 1323nm (λex = 442 nm, solid state) [Reaction Scheme 77]
Figure imgf000091_0001
Example Preparation of Yb 3+ [G-l]3- porphyrin (phenyl) 3 (COO~) zinc] 3 (terpyridine) (Reaction Scheme 78)
The title compound was prepared in the same manner as in Example 3, using [ [G-l] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er3+- [ [G-l] 3- porphyrin (phenyl) 3 (COO") zinc] 3 (terpyridine) ■ and Nd3+- [ [G-l] 3- porphyrin (phenyl) 3 (COO") zinc] 3 (terpyridine) were prepared in the same manner.
Yb3+- [ [G-l] 3-porphyrin (phenyl) 3 (COO") zinc] 3 (terpyridine) λe
978 nm (λex = 442 nm, solid state)
Er3+- [ [G-l] 3-porphyrin (phenyl) 3 (COO") zinc] 3.(terpyridine) λe
1520 nm (λex = 442 n , solid state)
Nd3+- [ [G-l] 3-porphyrin (phenyl) 3 (COO") zinc] 3 (terpyridine) λe
890, 1052, 1323 nm (λex = 442 nm, solid state)
Example 69 : Preparation of Yb 3+ [6-2] 3- porphyrin (phenyl ) 3 (COO") zinc] 3 (terpyridine ) (Reaction Scheme 78 ) The . title compound was prepared in the same manner as in
Example 3 , using [ [G-2 ] 3-5 , 10 , 15-triphenyl-20- ( 4- carboxyphenyl)porphtrin] zinc. Also, Er3+- [ [G-2] 3- porphyrin (phenyl) 3 (COO") zinc] 3(terpyridine) and Nd3+- [ [G-2] 3- porphyrin (phenyl) 3 (COO") zinc] 3 (terpyridine) were prepared in the same manner. Yb3+-[ [G-2] 3-porphyrin (phenyl) 3 (COO") zinc] 3 (terpyridine) : λem = 978 nm (λex = 442 nm, solid state)
Er3+-[ [G-2] 3-porphyrin (phenyl) 3 (COO") zinc] 3 (terpyridine) : λem = 1520 nm (λex = 442 nm, solid state)
Nd3+-[ [G-2] 3-porphyrin (phenyl) 3 (COO") zinc] 3 (terpyridine) : λem = 890, 1052, 1323 nm (λex = 442 nm, solid state)
Example 70: Preparation of Yb3+- [ [G-3] 3- porphyrin (phenyl) 3 (COO") zinc] 3 (terpyridine) (Reaction Scheme 78)
The title compound was prepared in the same manner as in Example 3, using [ [G-3] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er3+- [ [G-3] 3- porphyrin (phenyl) 3 (COO~) zinc] 3 (terpyridine) and Nd3+- [ [G-3] 3- porphyrin (phenyl) 3 (COO~) zinc] 3 (terpyridine) were prepared in the same manner. Yb3+- [ [G-3] 3-porphyrin (phenyl) 3 (COO") zinc] 3 (terpyridine) : λem = 978 nm (λex = 442 nm, solid state)
Er3+- [ [G-3] 3-porphyrin (phenyl) 3 (COO") zinc] 3 (terpyridine) : λem = 1520 nm (λex = 442 nm, solid state) Nd3+- [ [G-3] 3-porphyrin (phenyl) 3 (COO") zinc] 3 (terpyridine) : λem = 890, 1052, 1323 nm (λex = 442 n , solid state)
Example 71 : Preparation of Yb3+- [ [G-4 ] 3- porphyrin (phenyl ) 3 ( COO~) zinc] 3 ( terpyridine) (Reaction Scheme 78 )
The title compound was prepared in the same manner as in Example 3, using [ [G-4] 3~5, 10, 15~triphenyl-20- (4- carboxyphenyl) porphyrin] zinc. Also, Er3+- [ [G-4] 3- porphyrin (phenyl ) 3 (COO") zinc] 3 (terpyridine ) and Nd3+- [ [G-4 ] 3- porphyrin (phenyl ) 3 (COO") zinc] 3 (terpyridine ) were prepared in the same manner .
Yb3+- [ [G-4 ] 3-porphyrin (phenyl ) 3 (COO") zinc] 3 (terpyridine) : λem =
978 nm (λex = 442 nm, solid state) E Err33++-- [[ [[GG--44 ]] 33--ppoorrpphhyyrriinn ((pphheennyyll)) 33 ((CCOOCO ) zinc] 3 (terpyridine) : λe 1520 nm (λex = 442 nm, solid state)
N Idd33++-- [[ [[GG--44 ]] 33--ppoorrpphhyyrriinn ((pphheennyyll )) 33 ((CCOOOO" ) zinc] 3 (terpyridine) : λe 190 , 1052 , 1323 nm (λex = 442 nm, solid state )
Example 72j Preparation of Er - [ [G-l ] 3- porphyrin (phenyl ) 3 ( COO") platinum] 3 (terpyridine ) (Reaction Scheme
78 ) -
The title compound was prepared in the same manner as in Example 3, using [ [G-l]3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum. Also, Er3+- [ [G-l] 3- porphyrin (phenyl) 3 (COO~) platinum] 3 (terpyridine) and Nd3+- [ [G-l] 3- porphyrin (phenyl) 3 (COO~) platinum] 3 (terpyridine) were prepared in the same manner. Yb3+- [ [G-l] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (terpyridine) : λem
= 978 nm (λex = 442 nm, solid state)
Er3+- [ [G-l] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (terpyridine) : λem
= 1524 nm (λex = 442 nm, solid state)
Nd3+-[ [G-l] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (terpyridine) : λem = 890, -1052, 1323 nm (λex = 442 nm, solid state)
Example 73 Preparation of Yb3+- [ [G-2]3- porphyrin (phenyl) 3 (C00~) platinum] 3 (terpyridine) (Reaction Scheme 78) The -title compound was prepared in the same manner as in Example 3, using [ [G-2] 3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum. Also, Er3+- [ [G-2] 3- porphyrin (phenyl ) 3 (COO") platinum] 3 (terpyridine ) and Nd3+- [ [G-2 ] 3- porphyrin (phenyl) 3 (COO") platinum] 3 (terpyridine) were prepared in the same manner. Yb3+- [ [G-2] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (terpyridine) : λem =' 978 nm (λex = 442 nm, solid state)
Er3+-[ [G-2] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (terpyridine) : λem = 1524 nm (λex = 442 nm, solid state)
Nd3+-[ [G-2] 3-porphyrin (phenyl ) 3 (C00~) platinum] 3 (terpyridine) : λem = 890, 1052, 1323 nm (λex = 442 nm, solid state)
Example 74 Preparation of Yb3+- [ [G-3]3- porphyrin (phenyl) 3 (COO") platinum] 3 (terpyridine) (Reaction Scheme 78) The title compound was prepared in the same manner as in Example 3, sing [ [G-3] 3-5, 10, 15-triphenyl-20- (4- ' carboxyphenyl) porphyrin] latinum. Also, Er3+- [ [G-3] 3- porphyrin (phenyl) 3 (COO") platinum] 3 (terpyridine) and Nd3+- [ [G-3] 3- porphyrin (phenyl) 3 (C00~) platinum] 3 (terpyridine) were prepared in the same manner .
Yb3+- [ [G-3] 3-porphyrin (phenyl) 3 (COO~) platinum] 3 (terpyridine) : λem = 978. nm (-\ex = 442 nm, solid state)
Er3+- [ [G-3] 3-porphyrin (phenyl) 3 (C00~) platinum] 3 (terpyridine) : λem = 1524 nm (λex = 442 nm, solid state) Nd3+- [ [G-3] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (terpyridine) : λem = 890, 1052, 1323 nm (λex = 442 nm, solid state)
Example 75_: Preparation of Yb3+- [ [G-4] 3- porphyrin (phenyl) 3 ( COO") platinum] 3 (terpyridine) (Reaction Scheme 78) The title compound was prepared in the same manner as in Example 3, ' using [ [G-4]3-5, 10, 15-triphenyl-20- (4- carboxyphenyl) porphyrin] platinum. Also, Er3+- [ [G-4] 3- porphyrin (phenyl) 3 (COO") platinum] 3 (terpyridine) and Nd3+- [ [G-4]3- porphyrin (phenyl) 3 (COO") platinum] 3 (terpyridine) were prepared in the same manner.
Yb3+- [ [G-4 ] 3-porphyrin (phenyl) 3 (COO") platinum] 3 (terpyridine) λe = 978 nm (λex = 442 nm, solid state)
Er3+- [ [G-4] 3-porphyrin (phenyl) 3 (COO~) platinum] 3 (terpyridine) λ. = 1524 nm (λex = 442 nm, solid state)
Nd3+-[ [G-4] 3-porphyrin (phenyl) 3 (COO~) platinum] 3 (terpyridine) λP = 890, 1052, 1323 nm (λex = 442 nm, solid state)
[Reaction Scheme 78]
Figure imgf000095_0001
Example 76: Photoluminescent properties of rare earth complex compounds
Ln3+- ( [NA-1] 2-C02 ~) 3 (bipyridine). was added to a polymer material of. polymethylmethacrylate at amounts of 3 wt%, 5 wt%, 10 wt%, 15 wt%, 18 wt% and 20 wt% relative to the polymer material. The mixture was dissolved in a chloroform solvent having a weight corresponding to 10 times the weight of the mixture, to prepare a solution. This solution was coated on a quartz substrate by a spin-coating process to form a polymer thin -film. The formed thin film was irradiated with a 325-nm wavelength laser beam from a helium-cadmium (He-Cd) laser and measured for the photoluminescence intensities at the following wavelengths : ( 1 ) the photoluminescence intensity at a 978-nm wavelength, which corresponds to an electronic transition of 4F3/2 -> I11/2 that is the photoluminescent property of ytterbium (Yb ) ions ; ( 2 ) the photoluminescence intensity at a 1530-nm wavelength, which corresponds to an electronic transition of Ii3/2 -> I15/2 that is the photoluminescent property of erbium (Er) ions ; and ( 3 ) the photoluminescence intensity at a 1052-nm wavelength, which corresponds to an electronic transition of 2F5/2 -> F7/2 that is the photoluminescent property of Nd ions . The results showed that the photoluminescence intensity was increased with an increase in the content of the. complex compound, and when the content of the erbium complex was increased to 15% , the photoluminescence intensity at peak photoluminescence wavelength of erbium ions was 40 times increased . Also, it could be found that the polymer thin film doped with the erbium complexes exhibited at least 30 times higher photoluminescence intensity than that of the silica optical fiber doped with rare earth ions , and thus had high optical amplification effect . Also, it could be found that this effect was shown also in the case of the ytterbium and Nd complexes .
Example 77 : Photoluminescence properties of rare earth complex compounds
Ln3+- [ [G-2 ] 3-porphyrin (phenyl ) 3 (COO") platinum] 3 (terpyridine ) was added to a polymer material of polymethylmethacrylate at amounts of 3 wt% , 5 wt% , 10 wt% , 15 wt% , 18 wt% and 20 wt% relative to the polymer material . The mixture was dissolved in a chloroform solvent having a weight corresponding to 10 times the weight of the mixture, to prepare a solution. This solution was coated on a quartz substrate by a spin-coating process to form a polymer thin film. The formed thin film was irradiated with a 442-nm wavelength laser beam from a helium-cadmium (He-Cd) laser and measured for the photoluminescence intensities at the following wavelengths: (1) the photoluminescence intensity at a 978-nm wavelength, which corresponds to an electronic transition of F3/2 -> In/2 that is the photoluminescent property of ytterbium (Yb) ions; (2) the photoluminescence intensity at a 1530-nm wavelength, which corresponds to an electronic transition of 4Ii3/ -> Ii5/2 that is the photoluminescent property of erbium (Er) ions; and (3) the photoluminescence intensity at a 1052-nm wavelength, which corresponds to an electronic transition of 2F5/2 -> 4F/2 that is the photoluminescent property of Nd ions. The results showed that the photoluminescence intensity was increased with an increase in the content of the complex compound, and when the content of the erbium complex was increased to 15%, the photoluminescence intensity at peak photoluminescence wavelength of erbium ions was 125 times increased. Also, it could be found that the polymer thin film doped with the erbium complex exhibited at least 30 times higher photoluminescence intensity than that of the silica optical fiber doped with rare earth ions, and thus had high optical amplification effect. Also, it could be found that this effect was shown also in the case of the ytterbium and Nd complexes.
As a result, it can be found that the rare earth ion- containing porphyrin complexes of the present invention have an excellent light-harvesting effect and an excellent solubility in polymer medium and do not show the aggregation phenomenon and thus interaction between the rare earth metal ions. This suggests that the complexes of the present invention have a very excellent optical amplification effect. Also, the present invention makes it possible to prepare the rare earth ion- organic ligand complexes whose photophysical properties can be controlled such that light can be • amplified at various wavelengths as shown in FIG. 6. Particularly, as apparent from Example 77 and FIGS. 2 to 5, the dendritic complexes have very high photoluminescence intensities at the respective wavelengths. This indicates that the compounds of the present invention have very excellent optical amplification properties.
Industrial Applicability
In the existing method of doping the silica optical fiber with Er3+ ions, the doping concentration of Er3+ was limited to about 100-1,000 ppm. When the concentration exceeds this limit, a non-light-emitting process will generally occur to cause a rapid reduction in optical amplification efficiency. For this reason, it is impossible to perform high-gain optical amplification, and thus, it is difficult to achieve an optical amplification of about 30 dB in the form of planar waveguide- type optical integrated circuits.
Furthermore, many researches on the development of optical amplifier materials comprising an inorganic or organic polymer medium doped with rare earth ions, such as Er3+, or chelate complexes, have been conducted up to now. However, in such prior optical amplifier materials, an effect of high optical amplification cannot be achieved since the doping concentration of the rare earth metals is limited due to the low solubility of the rare earth metals in the polymer medium. Also, if the rare earth metals are used at high doping concentration, the aggregation between the metal ions and also the phase separation between the rare earth ions and the silica medium will occur to cause a reduction in optical amplification effect.
On the other hand, the present invention makes it possible to solve such problems occurring in the prior art. Namely, the present invention provides the rare earth ion-containing porphyrin complex compounds, which have a light-harvesting effect as shown in FIG. 1, and do not show the aggregation between the rare earth metals and thus the interaction between the rare earth metal ions. Also, as shown in FIG. 5, the dendritic complexes of the present invention have several times higher optical amplification effect than that of the prior material doped with the rare earth ions.
In addition, the present invention makes it possible to prepare the rare earth metal-containing organic ligand complex compounds whose photophysical properties can be controlled by suitable selection of the rare earth metal such that light at various wavelengths can be amplified as shown in FIG. 6.

Claims

What Is Claimed Is :
1. A rare earth ion-containing complex compound having a structure represented by the following formula :
Figure imgf000100_0001
wherein Ln is Yb, Er or Nd; a is 0, 1 or 2; B is
Figure imgf000100_0002
R is
Figure imgf000100_0003
R' is. CH3,
Figure imgf000101_0001
Figure imgf000101_0002
Figure imgf000101_0003
M is Zn or Pt; and Ra is H or F.
2. The rare earth ion-containing complex compound of Claim 1, which have a structure represented by the following chemical formula:
Figure imgf000101_0004
3. The rare earth ion-containing complex compound of Claim 1, which have a structure represented by the following chemical formula:
Figure imgf000101_0005
wherein x is 1 or 2.
4. The rare earth ion-containing complex compound of Claim 1, which have a structure represented by the following chemical formula :
Figure imgf000102_0001
wherein -x is 1 or 2
5. The rare earth ion-containing complex compound of Claim 1, which have a structure represented by the following chemical formula:
Figure imgf000102_0002
6. The rare earth ion-containing complex compound of Claim 1, which have a structure represented by the following chemical formula:
Figure imgf000102_0003
7. The rare earth ion-containing complex compound of Claim 1, which have a structure represented by the following chemical formula :
Figure imgf000103_0001
8. The rare earth ion-containing complex compound of Claim 1, which have a structure represented by the following chemical formula:
Figure imgf000103_0002
9. The rare earth ion-containing complex compound of Claim 1, which have a structure represented by the following chemical formula:
Figure imgf000103_0003
10. The rare earth ion-containing complex compound of Claim 1, which have a structure represented by the following chemical formula:
Figure imgf000104_0001
11. A method for preparing the rare earth ion-containing complex compound of Claim 1, the method comprising the steps of:
(a) adding KH and B-C02H (where B has the same means as defined in Claim 1) and • one selected from terpyridine and bipyridine to a vacuum-dried flask under a nitrogen stream;
(b) dissolving the mixture in an organic solvent;
(c) stirring the solution until hydrogen gas is not generated; and then adding a solution containing anhydrous ErCl3 and a small amount of water to the flask by a cannula and stirring the resulting solution for one day; and
(d) removing the solvent under vacuum and then washing the residue several '.times with diethyl ether.
12. A polymer blend having excellent photoluminescence intensity, which contains the rare earth ion-containing complex compound according to one of Claims 1 to 10.
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