CN103130839A - Ferrocene formamide type compound and preparation method and application thereof - Google Patents
Ferrocene formamide type compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN103130839A CN103130839A CN2013100348142A CN201310034814A CN103130839A CN 103130839 A CN103130839 A CN 103130839A CN 2013100348142 A CN2013100348142 A CN 2013100348142A CN 201310034814 A CN201310034814 A CN 201310034814A CN 103130839 A CN103130839 A CN 103130839A
- Authority
- CN
- China
- Prior art keywords
- ferrocene
- formula
- type compound
- aprotic solvent
- formamide type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention discloses a ferrocene formamide type compound presented as formula (I) and application of a preparation method for the ferrocene formamide type compound in three-order nonlinearity optics. The preparation method for the ferrocene formamide type compound has the advantages of being few in reaction steps, prone to obtain raw materials, simple in synthetic process, moderate in reaction condition and the like. Meanwhile, the preparation method for the ferrocene formamide type compound exploits the application of the ferrocene formamide type compound in three-order nonlinearity optics and has great implementation value and good social economic benefit. R in the formula (I) is phenyl which replaces phenyl or naphthyl or benzothiazolyl or replaces benzothiazolyl, substitutional group on the substitutional phenyl is halogen or methyl or nitro, and substitutional group on the substitutional benzothiazolyl is halogen or methyl or nitro.
Description
(1) technical field
The present invention relates to a kind of ferrocene formamide type compound and preparation method thereof and application in third order non-linear optical material, belong to field of functional materials.
(2) background technology
Nonlinear optical material can be applicable to optical communication, photometry calculation, optical information processing, optical storage and holography, laser processing, laser medicine, laser printing, laser telecine, laser device, laser controlled thermonuclear reaction and many aspects such as laser isotope separation, laser guidance, range finding and directed energy weapon.
The eighteen-electron rule that meets transition metal Cheng Jian due to ferrocenyl, show stability and the aromaticity of height, electronics in its frontier orbit is by the d electron feedback of iron atom, the d track participates in and has enlarged the π-electron system of metallocene ring, and iron atom also has various oxidation state and luxuriant loops and closes rear whole ferrocene group and become good electron-donating group.When it is connected with acceptor by pi-conjugated system, be easy to occur intramolecular charge and shift, and the Method Based on Asymmetric of induction system effectively, conjugated system is expanded and extended as much as possible, thereby molecule have larger non-linear susceptibility.Common π-electron conjugated bridge comprises carbon-carbon double bond (-C=C-), carbon-to-nitrogen double bon (-C=N-), and wherein the carbon-carbon double bond report is more.The electrophilic part of push-and-pull system is selected the color bodiess such as aromatic ring, fragrant heterocycle usually, and some organic pigment color bodiess with large pi-conjugated structure are the good integral parts that build Developments of Third-order Nonlinear Optical Polymers.Non-linear optical property research for ferrocene metalloid organic materials in early days mainly concentrates on the second order performance.Along with deepening continuously of research, the third order non-linear optical property of ferrocene metalloid organic materials just progressively becomes the focus of research.
Bin in 2008, and the people such as Y.J. (Chinese Physics Letters2008,25 (9), 3257-3259) report a kind of compound (shown in formula (1)) that contains the ferrocene structure of phthalocyanine, and used the degeneration four-wave mixing technology, be 2 * 10 in concentration
-5In M tetrahydrofuran (THF) (THF) solution, wavelength is 800nm, and frequency range is 50fs, and pulse-repetition is under the 1Hz condition, records the third-order non-linear coefficient χ of this compound
(3)γ is respectively 6.44 * 10 with molecular hyperpolarizability
-14Esu and 1.74 * 10
-30Esu, and compare with the molecular hyperpolarizability γ of the related compound of bibliographical information, find that the compound of this structure has higher molecular hyperpolarizability.
People's (chemical journals 2008 such as Zhou Xiaoli in 2008,66 (7), 775-782) synthesize ferrocene methylene radical triazole and transition metal cadmium and nickel and formed two kinds of different title complexs, use the YAG frequency double laser, pulse width is 7nm, the Z-scan measuring technology records its third-order non-linear specific refractory power.And the structure of material and the relation of performance be discussed, the non-linear optical property of finding material depends primarily on part (color bodies), simultaneously, owing to existing a methylene radical between the ferrocene group of part (color bodies) and triazole group, block the electronics transmission between ferrocene group and triazole group, failed to form larger conjugated system.Therefore, when metallic ion coordination was to the part, due to the existence of methylene radical, central metallic ions can not make a significant impact the Nonlinear Third-Order Optical Properties of part, thereby two kinds of compounds have similar nonlinear optics behavior.
Li in 2007, J.P. wait people (Journal of Organometallic Chemistry2007,692 (7), 1584-1592) studied between ferrocenyl benzoic acid respectively with the third order non-linear optical property of three kinds of transition metal lead (Pd), zinc (Zn) and manganese (Mn) title complex.Use the Z-scan detection method, pulsewidth is 8ns, and wavelength is 532nm, records the third-order nonlinear susceptibility χ of three kinds of title complexs in DMF solution
(3)Be respectively 6.19 * 10
-13Esu(Pd), 5.9 * 10
-13Esu(Zn) and 5.3 * 10
-13Esu(Mn).
Rangel-Rojo in 2003, R., Deng people (Optics Communications2003,228 (1-3), 181-186) report the Shiff base derivative (shown in formula (2)) that a naphthoquinones and triazole and ferrocene form, and used the Z-scan measuring technology, the YAG laser apparatus, frequency range is 10ps, has investigated the third order non-linear optical property of this material under different detection wavelength.Find that there is a metal ligand transfer absorbed in this material under 560nm.
(3) summary of the invention
The object of the invention is to provide a kind of ferrocene formamide type compound and preparation method thereof and application in third-order nonlinear optical.
The technical solution used in the present invention is:
The invention provides the compound of ferrocene formamide type shown in a kind of formula I,
In formula I: R is phenyl, substituted-phenyl, naphthyl, benzothiazolyl or substituted benzene benzothiazolyl, substituting group on described substituted-phenyl is halogen, methyl or nitro, substituting group on described substituted benzene benzothiazolyl is halogen, methyl or nitro, preferred R is substituted-phenyl or substituted benzene benzothiazolyl, substituting group on described substituted-phenyl is chlorine, fluorine, methyl or nitro, and the substituting group on described substituted benzene benzothiazolyl is nitro.
Further, described ferrocene formamide type compound is preferably one of following:
The present invention also provides a kind of preparation method of described ferrocene formamide type compound, and described method is: the ferrocene formyl chloride shown in formula (II) is dissolved in aprotic solvent A, obtains ferrocene formyl chloride solution; Aromatic amine shown in formula (III) is dissolved in aprotic solvent B, under acid binding agent exists, drip described ferrocene formyl chloride solution under-10～20 ℃, after reacting completely, with the reaction solution aftertreatment, the ferrocene formamide type compound shown in acquisition formula (I); Described acid binding agent is one of following: sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, pyridine or triethylamine (preferred sodium carbonate, sodium bicarbonate, sodium hydroxide or triethylamine); Described aprotic solvent A is one of following: methylene dichloride, ethylene dichloride, chloroform, tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO), tetramethylene sulfone or acetonitrile (preferred ethylene dichloride, chloroform, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), tetramethylene sulfone or acetonitrile), and described aprotic solvent B is identical with aprotic solvent A;
In formula (III): R is phenyl, substituted-phenyl, naphthyl, benzothiazolyl or substituted benzene benzothiazolyl, and the substituting group on described substituted-phenyl is halogen, methyl or nitro, and the substituting group on described substituted benzene benzothiazolyl is halogen, methyl or nitro.
Further, described ferrocene formyl chloride is 1:1.0～2.0:1.5～3.5 with the ratio of the amount of substance that feeds intake of aromatic amine and acid binding agent, preferred 1:1.2～1.5:2.0～3.0.
Further, described ferrocene formyl chloride and aprotic solvent A and aprotic solvent B total mass ratio are 1:100～300, preferred 1:150～200, described aprotic solvent A and aprotic solvent B volumetric usage separately get final product with dissolving, and preferred aprotic solvent A and aprotic solvent B volume ratio are 1:1.
Further, described reaction is to react 5～10h under-10～20 ℃, preferably reacts 6～8h under-5～5 ℃.
Further, described reaction solution post-treating method is: use the TLC tracking monitor in reaction process, namely react completely until ferrocene acyl chlorides point disappears, reaction solution is washed standing demix with saturated sodium bicarbonate solution, the water layer chloroform extraction, get and carry out silica gel column chromatography after the organic phase steaming desolventizes, the ethyl acetate take volume ratio as 1:5 and sherwood oil mixed solution collect as eluent the elutriant that contains target components, drying, ferrocene formamide type compound shown in acquisition formula (I).
further, the preparation method of described ferrocene formamide type compound carries out as follows: the ferrocene formyl chloride shown in formula (II) is dissolved in aprotic solvent A, obtains ferrocene formyl chloride solution, aromatic amine shown in formula (III) is dissolved in aprotic solvent B, under acid binding agent exists, drip described ferrocene formyl chloride solution under-5～5 ℃, reaction 6～8h, use the TLC tracking monitor in reaction process, until disappearing, ferrocene acyl chlorides point namely reacts completely, reaction solution is washed with saturated sodium bicarbonate solution, standing demix, the water layer chloroform extraction, get and carry out silica gel column chromatography after the organic phase steaming desolventizes, ethyl acetate take volume ratio as 1:5 and sherwood oil mixed solution are as eluent, collection contains the elutriant of target components, dry, ferrocene formamide type compound shown in acquisition formula (I), described acid binding agent is one of following: sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, pyridine or triethylamine, described aprotic solvent A is one of following: methylene dichloride, ethylene dichloride, chloroform, tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO), tetramethylene sulfone or acetonitrile, and described aprotic solvent B is identical with aprotic solvent A, described ferrocene formyl chloride is 1:1.2～1.5:2.0～3.0 with the ratio of the amount of substance that feeds intake of aromatic amine and acid binding agent, and described ferrocene formyl chloride and aprotic solvent A and aprotic solvent B total mass ratio are 1:150～200.
The invention still further relates to the application of a kind of described ferrocene formamide type compound in third-order nonlinear optical.
After ferrocene access amide group, directly be connected to the nitrogen-atoms with lone-pair electron due to the carbon atom on carbonyl, it is pi-conjugated that n electronics on nitrogen-atoms and the π-electron on carbonyl have produced n-, cause the raising of π orbital energy level, reduce the energy level difference with π * track, be conducive to improve molecule divalence Nonlinear hyperpolarizability γ value.The lone-pair electron of N atom can be pi-conjugated with the conjugated system formation p-of material molecule simultaneously, between two keys that π-electron connects by iron alkene center and key and fragrant heterocycle color bodies, delocalization occurs, thereby strengthen the electronics mobility of whole molecule, increase the delocalization degree of electronics, reduce n-π * and the π-π * transition energy of material molecule, thereby improve the non-linear optical property of material.
Ferrocene formamide type compound shown in formula I of the present invention and in the application in third-order nonlinear optical field: adopt the test of degeneration four-wave mixing (DFWM) method, take the Ti:Sapphire femto-second laser as light source.
The third-order nonlinear susceptibility χ of sample
s (3)Obtain by Relative detecting method, namely adopt generally acknowledged dithiocarbonic anhydride as a reference under the same conditions, obtain the third-order nonlinear susceptibility χ of sample by the signal magnitude of comparative sample and dithiocarbonic anhydride
s (3), calculated by following formula:
L in formula (1)
sAnd L
rBe respectively testing sample with reference to the cuvette thickness of sample dithiocarbonic anhydride, n
sAnd n
rBe respectively testing sample with reference to the specific refractory power of sample dithiocarbonic anhydride, χ
sAnd χ
rBe respectively testing sample with reference to the third-order nonlinear susceptibility of sample dithiocarbonic anhydride, I
sAnd I
rBe respectively testing sample with reference to the conjugate beam intensity of sample dithiocarbonic anhydride, α is linear absorption coefficient, with reference to the χ of sample dithiocarbonic anhydride
r (3)Be 6.7 * 10
-14Esu, n
rBe 1.632.
Testing sample is calculated by following formula by the nonlinear refractive index that the third-order non-linear coefficient causes:
n
2(esu)=12 π χ
(3)/ n
2Formula (2)
In formula (2), n
2Nonlinear refractive index for test substance; χ
(3)Be the third-order nonlinear susceptibility of test substance, the χ that namely calculates
s (3)N is the linear refractive index of test substance;
The second hyperpolarizabilitieof γ of sample solute molecule can be tried to achieve by formula (3):
In formula (3), N is the molecular density of solute, N=6.02 * 10
23C, c are the volumetric molar concentration of sample solution, f
4Be local fields modifying factor, f
4=[(n
s 2+ 2)/3]
4, wherein n is the linear refractive index of test substance.
Time of response τ (fs) is by the mapping of four-wave mixing conjugate beam intensity and time of lag, then obtains after Gauss curve fitting.
Compared with prior art, beneficial effect of the present invention is mainly reflected in: it is few that the inventive method has reactions steps, the advantages such as raw material is easy to get, synthesis technique is simple, reaction conditions is gentle, open up simultaneously the application of ferrocene formamide type compound in third-order nonlinear optical, had larger implementary value and good economic results in society.
(4) description of drawings
Fig. 1 for the nonlinear optical response of the ferrocene formamide type compound shown in the formula (I-1) that detects embodiment 1 preparation with degeneration four-wave mixing to scheming time of lag, ordinate zou is four-wave mixing conjugation intensity, X-coordinate is time of lag, the figure mid point is experimental data, solid line is the Gauss curve fitting result, and after match, the peak width at half height of response peak is time of response τ; Peak height is the light intensity I described in formula (1).
Fig. 2 be the ferrocene formamide type compound shown in the formula (I-1) of embodiment 1 preparation proton nmr spectra (
1H NMR) spectrogram.
Fig. 3 is mass spectrum MS (ESI) spectrogram of the ferrocene formamide type compound shown in the formula (I-1) of embodiment 1 preparation.
Fig. 4 for the nonlinear optical response of the ferrocene formamide type compound shown in the formula (I-2) that detects embodiment 2 preparations with degeneration four-wave mixing to scheming time of lag.
Fig. 5 be the ferrocene formamide type compound shown in the formula (I-2) of embodiment 2 preparation proton nmr spectra (
1H NMR) spectrogram.
Fig. 6 is mass spectrum MS (ESI) spectrogram of the ferrocene formamide type compound shown in the formula (I-2) of embodiment 2 preparation.
Fig. 7 for the nonlinear optical response of the ferrocene formamide type compound shown in the formula (I-3) that detects embodiment 3 preparations with degeneration four-wave mixing to scheming time of lag.
Fig. 8 be the ferrocene formamide type compound shown in the formula (I-3) of embodiment 3 preparation proton nmr spectra (
1H NMR) spectrogram.
Fig. 9 is mass spectrum MS (ESI) spectrogram of the ferrocene formamide type compound shown in the formula (I-3) of embodiment 3 preparation.
Figure 10 for the nonlinear optical response of the ferrocene formamide type compound shown in the formula (I-4) that detects embodiment 4 preparations with degeneration four-wave mixing to scheming time of lag.
Figure 11 be the ferrocene formamide type compound shown in the formula (I-4) of embodiment 4 preparation proton nmr spectra (
1H NMR) spectrogram.
Figure 12 is mass spectrum MS (ESI) spectrogram of the ferrocene formamide type compound shown in the formula (I-4) of embodiment 4 preparation.
Figure 13 for the nonlinear optical response of the ferrocene formamide type compound shown in the formula (I-5) that detects embodiment 5 preparations with degeneration four-wave mixing to scheming time of lag.
Figure 14 be the ferrocene formamide type compound shown in the formula (I-5) of embodiment 5 preparation proton nmr spectra (
1H NMR) spectrogram.
Figure 15 is mass spectrum MS (ESI) spectrogram of the ferrocene formamide type compound shown in the formula (I-5) of embodiment 5 preparation.
Figure 16 for the nonlinear optical response of the ferrocene formamide type compound shown in the formula (I-6) that detects embodiment 6 preparations with degeneration four-wave mixing to scheming time of lag.
Figure 17 be the ferrocene formamide type compound shown in the formula (I-6) of embodiment 6 preparation proton nmr spectra (
1H NMR) spectrogram.
Figure 18 is mass spectrum MS (ESI) spectrogram of the ferrocene formamide type compound shown in the formula (I-6) of embodiment 6 preparation.
Figure 19 for the nonlinear optical response of the ferrocene formamide type compound shown in the formula (I-7) that detects embodiment 7 preparations with degeneration four-wave mixing to scheming time of lag.
Figure 20 be the ferrocene formamide type compound shown in the formula (I-7) of embodiment 7 preparation proton nmr spectra (
1H NMR) spectrogram.
Figure 21 is mass spectrum MS (ESI) spectrogram of the ferrocene formamide type compound shown in the formula (I-7) of embodiment 7 preparation.
Figure 22 is that the present invention's degeneration four-wave mixing used detects index path.
Figure 23 for reference to the nonlinear optical response of sample dithiocarbonic anhydride to scheming time of lag.
Figure 24 is the UV, visible light absorption figure of synthetic 7 compounds that obtain of embodiment 1-7.
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
With 0.1212g (1.0mmol) 3,5-xylidine, 0.3g (2.83mmol) Na
2CO
3And 20mL(26.51g) anhydrous CH
2Cl
2, add in the there-necked flask of 100mL, be cooled to 0～5 ℃, drip 0.28g (1.0mmol) ferrocene formyl chloride and 20mL(26.51g) anhydrous CH
2Cl
2Mixed solution, under 0～5 ℃ the reaction 10 hours.The TLC tracking monitor namely reacts completely until ferrocene acyl chlorides point disappears, and reaction solution is added saturated NaHCO
3Solution, standing demix, water layer CH
2Cl
2Extraction, merge and carry out silica gel column chromatography after the organic phase steaming desolventizes, with the ethyl acetate of volume ratio 1:5 and sherwood oil mixed solution as eluent, according to hydrogen spectrum and mass spectrogram, collect the elutriant that contains target components, drying, obtain yellow solid 0.1389g, yield 41.7%, fusing point: 233-234 ℃, structure is as shown in (I-1).Proton nmr spectra (
1H NMR) spectrogram as shown in Figure 2, mass spectrum MS (ESI) spectrogram is as shown in Figure 3.Degeneration four-wave mixing detects the nonlinear optical response of the ferrocene formamide type compound shown in formula (I-1) to scheming (detection method is with embodiment 8) as shown in Figure 1 time of lag.
Take Ortho-Chloro aniline as raw material, input amount is 0.2552g (2.0mmol), acid binding agent changes sodium bicarbonate into, and input amount is 0.29g (3.45mmol), and solvent changes ethylene dichloride into, total input amount is 23mL(28.9g), other synthetic methods obtain yellow solid 0.1875g with embodiment 1, yield 55.2%, fusing point: 167-168 ℃, structure is as shown in (I-2).The nonlinear optical response that degeneration four-wave mixing detects the ferrocene formamide type compound shown in formula (I-2) is to figure time of lag (detection method is with embodiment 8) as shown in Figure 4, proton nmr spectra (
1H NMR) spectrogram as shown in Figure 5, mass spectrum MS (ESI) spectrogram is as shown in Figure 6.
Take m-chloro aniline as raw material, input amount is 0.1914g (1.5mmol), acid binding agent is used sodium hydroxide instead, input amount is 0.08g(2.0mmol), the total solvent amount changes 63mL(83.5g into), other synthetic methods are with embodiment 1, obtain yellow solid 0.2139g, yield 63.0%, fusing point: 211-212 ℃, structure is as shown in (I-3).The nonlinear optical response that degeneration four-wave mixing detects the ferrocene formamide type compound shown in formula (I-3) is to figure time of lag (detection method is with embodiment 8) as shown in Figure 7, proton nmr spectra (
1H NMR) spectrogram as shown in Figure 8, mass spectrum MS (ESI) spectrogram is as shown in Figure 9.
Take adjacent fluoroaniline as raw material, input amount is 0.1111g (1.0mmol), solvent changes tetrahydrofuran (THF) into, acid binding agent changes triethylamine into, and input amount is 0.152g(1.5mmol), other synthetic methods are with embodiment 1, obtain yellow solid 0.1790g, yield 55.4%, fusing point: 231-232 ℃, structure is as shown in (I-4).The nonlinear optical response that degeneration four-wave mixing detects the ferrocene formamide type compound shown in formula (I-4) is to figure time of lag (detection method is with embodiment 8) as shown in Figure 10, proton nmr spectra (
1H NMR) spectrogram as shown in Figure 11, mass spectrum MS (ESI) spectrogram is as shown in Figure 12.
Take m-nitraniline as raw material, input amount is 0.1381g (1.0mmol), temperature of reaction is-10～-5 ℃, solvent changes the DMF(dimethyl formamide into), other synthetic methods obtain brown solid 0.2378g with embodiment 1, yield 67.9%, fusing point: 196-197 ℃, structure is as shown in (I-5).The nonlinear optical response that degeneration four-wave mixing detects the ferrocene formamide type compound shown in formula (I-5) is to figure time of lag (detection method is with embodiment 8) as shown in Figure 13, proton nmr spectra (
1H NMR) spectrogram as shown in Figure 14, mass spectrum MS (ESI) spectrogram is as shown in Figure 15.
Take the 2-amino-6-nitrobenzothiazole as raw material, input amount is 0.1952g (1.0mmol), temperature of reaction changes 15～20 ℃ into, reaction times is 5 hours, and solvent changes tetramethylene sulfone into, and other synthetic methods are with embodiment 1, obtain yellow solid 0.0831g, yield 20.4%, fusing point: greater than 250 ℃, structure is as shown in (I-6).The nonlinear optical response that degeneration four-wave mixing detects the ferrocene formamide type compound shown in formula (I-6) is to figure time of lag (detection method is with embodiment 8) as shown in Figure 16, proton nmr spectra (
1H NMR) spectrogram as shown in Figure 17, mass spectrum MS (ESI) spectrogram is as shown in Figure 18.
Be raw material with 3,4,5-trifluoromethyl aniline, input amount is 0.1471g (1.0mmol), reaction times is 7 hours, and solvent changes acetonitrile into, and other synthetic methods obtain deep yellow solid 0.2331g with embodiment 1, yield 64.9%, fusing point: 185-186 ℃, structure is as shown in (I-7).The nonlinear optical response that degeneration four-wave mixing detects the ferrocene formamide type compound shown in formula (I-7) is to figure time of lag (detection method is with embodiment 8) as shown in Figure 19, proton nmr spectra (
1H NMR) spectrogram as shown in Figure 20, mass spectrum MS (ESI) spectrogram is as shown in Figure 21.
The third order non-linear optical property of ferrocene formamide type compound of the present invention adopts the test of degeneration four-wave mixing (DFWM) method.
As light source, wavelength is 800nm to adopt femto-second laser (Ti:Sapphire, German Nanolayers company produce), and pulsewidth is 80fs, and repetition rate is 1KHz, and single pulse energy is 0.05mJ.The third-order nonlinear susceptibility χ of sample
s (3)Obtain by relative side chain method, namely adopt under the same conditions the dithiocarbonic anhydride of generally acknowledging as reference, obtain the third-order nonlinear susceptibility χ of sample by the signal magnitude of comparative sample and dithiocarbonic anhydride
s (3)Circular is as follows:
L in formula (1)
s, L
rRepresent respectively testing sample with reference to the cuvette thickness of sample dithiocarbonic anhydride, n
s, n
rBe respectively testing sample with reference to the specific refractory power of sample dithiocarbonic anhydride, χ
sAnd χ
rBe respectively testing sample with reference to the third-order nonlinear susceptibility of sample dithiocarbonic anhydride, I
sAnd I
rBe respectively testing sample with reference to the conjugate beam intensity of sample dithiocarbonic anhydride, α is linear absorption coefficient, according to bibliographical information, with reference to the χ of sample dithiocarbonic anhydride
r (3)Be 6.7 * 10
-13Esu, n
rBe 1.632.
The chemical compounds I that embodiment 1～7 is prepared-1～I-7 are at 200～800nm place's test ultraviolet-visible absorption spectroscopy, as shown in Figure 24.The ultraviolet-visible absorption spectroscopy figure that is surveyed 7 compounds by Figure 24 as can be known, institute measures and monitor the growth of standing timber material in optical maser wavelength 800nm place's nothing absorption, show that its third order non-linear optical property can because electron resonance strengthens, not that is to say that the conjugate beam signal that detects is the third-order nonlinear optical signal under non-resonant condition under this detection wavelength in the DFWM experiment.Formula in (1) is
Therefore, formula (1) can be reduced to:
Simultaneously, because cuvette thickness is L
s=L
r=1mm, so formula (5) can be reduced to:
The linear absorption n of sample in formula (1-2)
sRecorded object of reference CS by Abbe refractometer
2N
rBe 1.632.
The nonlinear optical response of Figure 23 dithiocarbonic anhydride is the conjugate beam intensity I of dithiocarbonic anhydride to peak height in time of lag figure
sThe nonlinear optical response of institute's test sample product is the conjugate beam intensity I of corresponding each material to peak height in time of lag figure
rAbove data substitution formula (1-2) can be obtained the third-order nonlinear susceptibility χ of the material of measuring and monitoring the growth of standing timber
s (3)The nonlinear refractive index that is caused by the third-order non-linear coefficient is calculated by following formula:
n
2(esu)=12 π χ
(3)/ n
2Formula (2)
In formula (2), n
2Nonlinear refractive index for test substance; χ
(3)(esu) be the third-order nonlinear susceptibility of test substance, namely calculate the χ of gained
s (3)N is the linear refractive index of test substance;
The second hyperpolarizabilitieof γ of sample solute molecule can be tried to achieve by following formula:
In formula (3), N is the molecular density of solute, N=6.02 * 10
23C, c are the volumetric molar concentration of sample solution, f
4Be local fields modifying factor, f
4=[(n
2+ 2)/3]
4, n is the linear refractive index of test substance.
Test sample: it is 5 * 10 that the ferrocene formamide type compound suc as formula shown in (I-1)～(I-7) that the embodiment of the present invention 1～7 is prepared is made into concentration
-4The DMF(dimethyl formamide of mol/L) solution is as sample, then adopts degeneration four-wave mixing (DFWM) method to carry out the third order non-linear optical property test, and result is as shown in table 1, compound (I-1) conjugation light intensity and time of lag as shown in Figure 1:
Table 1 ferrocene formamide type compound third order non-linear optical property parameter
According to document The Journal of Physical Chemistry, 1990,94 (7): 2847-2851, (light source is the Nd:YAG laser apparatus to the employing femtosecond lasers such as Saswati Ghosal, wavelength 602nm, pulsewidth 400fs), to record the second hyperpolarizabilitieof (γ) of ferrocene molecule be 1.61 ± 0.18 * 10 to DFWM experiment light path
-35Esu contrasts as seen from Table 1, and ferrocene formamide type compound molecule second hyperpolarizabilitieof of the present invention than high 4 orders of magnitude of ferrocene precursor structure, is the very potential third order non-linear optical material of a class.
Claims (9)
1. ferrocene formamide type compound shown in a formula I,
In formula I: R is phenyl, substituted-phenyl, naphthyl, benzothiazolyl or substituted benzene benzothiazolyl, and the substituting group on described substituted-phenyl is halogen, methyl or nitro, and the substituting group on described substituted benzene benzothiazolyl is halogen, methyl or nitro.
2. ferrocene formamide type compound as claimed in claim 1 is characterized in that described compound is one of following:
3. the preparation method of the described ferrocene formamide type of claim 1 compound, is characterized in that described method is: the ferrocene formyl chloride shown in formula (II) is dissolved in aprotic solvent A, obtains ferrocene formyl chloride solution; Aromatic amine shown in formula (III) is dissolved in aprotic solvent B, under acid binding agent exists, drip described ferrocene formyl chloride solution under-10～20 ℃, after reacting completely, with the reaction solution aftertreatment, the ferrocene formamide type compound shown in acquisition formula (I); Described acid binding agent is one of following: sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, pyridine or triethylamine; Described aprotic solvent A is one of following: methylene dichloride, ethylene dichloride, chloroform, tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO), tetramethylene sulfone or acetonitrile, and described aprotic solvent B is identical with aprotic solvent A;
In formula (III): R is phenyl, substituted-phenyl, naphthyl, benzothiazolyl or substituted benzene benzothiazolyl, and the substituting group on described substituted-phenyl is halogen, methyl or nitro, and the substituting group on described substituted benzene benzothiazolyl is halogen, methyl or nitro.
4. the preparation method of ferrocene formamide type compound as claimed in claim 3, is characterized in that described ferrocene formyl chloride and the ratio of the amount of substance that feeds intake of aromatic amine and acid binding agent are 1:1.0～2.0:1.5～3.5.
5. the preparation method of ferrocene formamide type compound as claimed in claim 3, is characterized in that described ferrocene formyl chloride and aprotic solvent A and aprotic solvent B total mass ratio are 1:100～300.
6. the preparation method of ferrocene formamide type compound as claimed in claim 3, is characterized in that described reaction is to react 5～10h under-10～20 ℃.
7. the preparation method of ferrocene formamide type compound as claimed in claim 3, it is characterized in that described reaction solution post-treating method is: use the TLC tracking monitor in reaction process, until disappearing, ferrocene acyl chlorides point namely reacts completely, reaction solution is washed with saturated sodium bicarbonate solution, standing demix, the water layer chloroform extraction, get and carry out silica gel column chromatography after the organic phase steaming desolventizes, ethyl acetate take volume ratio as 1:5 and sherwood oil mixed solution are as eluent, collection contains the elutriant of target components, drying, ferrocene formamide type compound shown in acquisition formula (I).
8. the preparation method of ferrocene formamide type compound as claimed in claim 3 is characterized in that described reaction carries out as follows: the ferrocene formyl chloride shown in formula (II) is dissolved in aprotic solvent A, obtains ferrocene formyl chloride solution, aromatic amine shown in formula (III) is dissolved in aprotic solvent B, under acid binding agent exists, drip described ferrocene formyl chloride solution under-5～5 ℃, reaction 6～8h, use the TLC tracking monitor in reaction process, until disappearing, ferrocene acyl chlorides point namely reacts completely, reaction solution is washed with saturated sodium bicarbonate solution, standing demix, the water layer chloroform extraction, get and carry out silica gel column chromatography after the organic phase steaming desolventizes, ethyl acetate take volume ratio as 1:5 and sherwood oil mixed solution are as eluent, collection contains the elutriant of target components, dry, ferrocene formamide type compound shown in acquisition formula (I), described acid binding agent is one of following: sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, pyridine or triethylamine, described aprotic solvent A is one of following: methylene dichloride, ethylene dichloride, chloroform, tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO), tetramethylene sulfone or acetonitrile, and described aprotic solvent B is identical with aprotic solvent A, described ferrocene formyl chloride is 1:1.2～1.5:2.0～3.0 with the ratio of the amount of substance that feeds intake of aromatic amine and acid binding agent, and described ferrocene formyl chloride and aprotic solvent A and aprotic solvent B total mass ratio are 1:150～200.
9. the application of the described ferrocene formamide type of claim 1 compound in third-order nonlinear optical.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100348142A CN103130839A (en) | 2013-01-28 | 2013-01-28 | Ferrocene formamide type compound and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100348142A CN103130839A (en) | 2013-01-28 | 2013-01-28 | Ferrocene formamide type compound and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103130839A true CN103130839A (en) | 2013-06-05 |
Family
ID=48491336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100348142A Pending CN103130839A (en) | 2013-01-28 | 2013-01-28 | Ferrocene formamide type compound and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103130839A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108752327A (en) * | 2018-04-17 | 2018-11-06 | 浙江工业大学 | 3- (2- benzoxazoles) Diarbarone compound and its preparation method and application |
| CN112979718A (en) * | 2021-02-24 | 2021-06-18 | 厦门稀土材料研究所 | Ferrocenecarboxylic acid derivative, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020185634A1 (en) * | 1996-11-12 | 2002-12-12 | Seth Marder | Two-photon or higher-order absorbing optical materials and methods of use |
| US7481955B2 (en) * | 2006-05-31 | 2009-01-27 | Transitions Optical, Inc. | Photochromic materials comprising metallocenyl groups |
| CN102010446A (en) * | 2010-11-09 | 2011-04-13 | 浙江工业大学 | Ferrocene schiff base derivative and preparation method and application thereof |
-
2013
- 2013-01-28 CN CN2013100348142A patent/CN103130839A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020185634A1 (en) * | 1996-11-12 | 2002-12-12 | Seth Marder | Two-photon or higher-order absorbing optical materials and methods of use |
| US7481955B2 (en) * | 2006-05-31 | 2009-01-27 | Transitions Optical, Inc. | Photochromic materials comprising metallocenyl groups |
| CN102010446A (en) * | 2010-11-09 | 2011-04-13 | 浙江工业大学 | Ferrocene schiff base derivative and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 陶晓敏: "酰胺型二茂铁系金属有机色素三阶非线性光学材料合成研究", 《浙江大学硕士学位论文》 * |
| 陶晓敏等，: "二茂铁酰胺类金属有机三阶非线性光学材料的合成", 《功能材料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108752327A (en) * | 2018-04-17 | 2018-11-06 | 浙江工业大学 | 3- (2- benzoxazoles) Diarbarone compound and its preparation method and application |
| CN108752327B (en) * | 2018-04-17 | 2020-11-13 | 浙江工业大学 | 3- (2-benzoxazole) coumarin amide compound and preparation method and application thereof |
| CN112979718A (en) * | 2021-02-24 | 2021-06-18 | 厦门稀土材料研究所 | Ferrocenecarboxylic acid derivative, preparation method and application thereof |
| CN112979718B (en) * | 2021-02-24 | 2022-10-28 | 厦门稀土材料研究所 | Ferrocenecarboxylic acid derivative, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Synthesis and third-order nonlinear optical properties of a sandwich-type mixed (phthalocyaninato)(schiff-base) triple-decker complexes | |
| Coe et al. | Combining very large quadratic and cubic nonlinear optical responses in extended, tris-chelate metallochromophores with six π-conjugated pyridinium substituents | |
| Shi et al. | Synthesis and second-order nonlinear optical properties of push-pull BODIPY derivatives | |
| Wang et al. | Third-order nonlinear optical properties of a novel series of D-π-A pyrene-aldehyde derivatives | |
| Erande et al. | Triphenylamine derived coumarin chalcones and their red emitting OBO difluoride complexes: Synthesis, photophysical and NLO property study | |
| Han et al. | Third-order nonlinear optical properties of cyanine dyes with click chemistry modification | |
| Razak | Synthesis, structure and optical limiting effect of two new nickel complexes containing strongly bound geometrically fixed multi-sulfur 1, 2-dithiolene ligands showing remarkable near-IR absorption | |
| Herbivo et al. | Synthesis and characterization of novel, thermally stable 2-aryl-5-dicyanovinylthiophenes and 5-aryl-5′-dicyanovinyl-2, 2′-bithiophenes as potentially promising non-linear optical materials | |
| Wang et al. | Cooperative enhancement of optical nonlinearities in a porphyrin derivative bearing a pyrimidine chromophore at the periphery | |
| Teimuri-Mofrad et al. | Design, synthesis and characterization of ferrocene based V-shaped chromophores with modified nonlinear effect | |
| CN102010446A (en) | Ferrocene schiff base derivative and preparation method and application thereof | |
| Liang et al. | Pyrene-Based Small Molecular Nonlinear Optical Materials Modified by ‘‘Click-Reaction’’ | |
| Teimuri-Mofrad et al. | Investigation of 5, 6-dimethoxy-1-indanone derivatives in optical applications: Synthesis, characterization and study of linear and nonlinear optical properties | |
| Kumar et al. | Optical properties of 3-substituted indoles | |
| Vishnumurthy et al. | Synthesis, electrochemical and optical studies of new cyanopyridine based conjugated polymers as potential fluorescent materials | |
| Hu et al. | Synthesis, characterization, and optical properties of new metal complexes with the multi-sulfur 1, 2-dithiolene ligand | |
| Cerquera et al. | Synthesis, characterization and photophysics of novel BODIPY linked to dumbbell systems based on Fullerene [60] pyrrolidine and Fullerene [60] isoxazoline | |
| Rahimpour et al. | Isophorone‐based organometallic chromophores: Synthesis, characterization and investigation of electro‐optical properties | |
| Heyer et al. | Step-by-step synthesis of multimodule assemblies engineered from BODIPY, DPP, and Triphenylamine Moieties | |
| CN103130839A (en) | Ferrocene formamide type compound and preparation method and application thereof | |
| Zhao et al. | Third-order nonlinear optical properties of the “clicked” closed-ring spiropyrans | |
| Miao et al. | The third-order nonlinear optical properties of charge flowable trimethine cyanine with quinolone groups | |
| Amala et al. | The synthesis of 3-ethyl-5-methyl-2, 6-diarylpiperidin-4-on-1-ium picrates and their spectral, XRD and theoretical studies | |
| Ge et al. | Third-order nonlinear optical properties of symmetric phenoxazinium chlorides with resonance structures at 532 nm | |
| Cai et al. | Degenerate four-wave mixing determination of third-order optical nonlinearities of three mixed ligand nickel (II) complexes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130605 |