WO2007071028A1

WO2007071028A1 - Compounds, complexes and uses thereof

Info

Publication number: WO2007071028A1
Application number: PCT/CA2006/002060
Authority: WO
Inventors: Robert Douglas Singer; Jitendra Harjani
Original assignee: St. Mary's University
Priority date: 2005-12-23
Filing date: 2006-12-19
Publication date: 2007-06-28

Abstract

There is provided compounds of formula (I): wherein R1, R2, R3, X1, X2, X3, can represent various substituents and m, n, p can be of various different values. These compounds can be useful for forming complexes. These compounds can in fact be used for complexing various metals. For example, they can be used for decontaminating a liquid by removing a metal comprised therein.

Description

COMPOUNDS, COMPLEXES AND USES THEREOF

TECHNICAL FIELD

The present invention relates to improvements in the field of organic chemistry. In particular, this invention relates to new compounds that can be useful as ligands and ionic liquids or for forming various complexes.

BACKGROUND OF THE INVENTION

Ionic liquids have been defined as any ionic compound that has a melting point lower than 100⁰C. The use of ionic liquids as solvents has been gaining substantial interest over the last several years. These new solvents have been touted as potential "Green Solvents" for a variety of industrial applications. The usefulness of these compounds as solvents lays in a number their physical properties that make them rather unique as compared to more traditional "molecular" or "covalent" solvents. Added functionality in ionic liquids enables them to perform specific tasks to exploit in various applications affording what are referred to as Task Specific ionic Liquids (TSIL's).

U. S Pat. No. 6,881 ,321 discloses a metal extraction process in which an ore containing a metallic element is treated with a chlorine gas so as to obtain a chloride of a metallic element. Such a chlorine metallic element is then mixed with an ionic liquid (1-butyl-methylimmidazolium chloride) so as to form an electrolyte. Finally, the metallic element is electrodeposited from the electrolyte thereby being extracted.

Notwithstanding the fact that several functionalities have been added to various types of ionic liquids in order to perform various specific tasks (Recent reviews include : (a) Olivier-Bourbigou, H. and Magna, L., J. MoI. Catal. A: Chem. 2002, 419, 182; (b) Wilkes, J.S., Green Chem. 2002, 4, 73; (c) Kumar, A., Chem. Rev. 2001 , 101 , 1; (d) Wasserschied, P. and Keim, W., Angew. Chem. Int. Ed. 2000, 39, 3772; (e) Welton, T., Chem. Rev. 1999, 99,

- i - 2071 ; (T) Holbrey, J. D. and Seddon, K.R., Clean Products and Processes 1999, 1 , 223; (g) Olivier, H., J. MoI. Catal. A: Chem. 1999, 146, 285.) , it seems that so far no solution have been proposed concerning ionic liquids that could be used for chelating metals i.e. for forming complexes with such metals. It would thus be highly desirable to be provided with compounds that could be used as ligands for chelating metal ions while simultaneously being classified as ionic liquids

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide compounds that would overcome the above-mentioned drawbacks.

It is another object of the present invention to provide compounds that could have simultaneously the properties of ionic liquids and of ligands.

It is another object of the present invention to provide ionic liquids that could be capable of chelating metals or of forming complexes with such metals.

It is another object of the present invention to provide a process for preparing such compounds.

It is another object of the present invention to provide complexes or chelates made of ionic liquids and metal, which could be used as catalyst.

It is another object of the present invention to provide a metal extraction process.

It is another object of the present invention to provide a method for removal of a contaminating metal. It is another object of the present invention to provide a method for decontaminating a liquid by removing a metal therefrom.

According to one aspect of the invention, there is provided compounds of formula (I):

Θ ® x¹

m X² (I)

wherein R¹ is a positively charged heterocyclic ring, which is unsubstituted or substituted with 1 to 3 substitutents selected from the group consisting of halogen atom, -NO₂, -CN -OH, -CF₃ -COR⁴, -SH, -OMe, -SMe, - SPh, -COOH, -COOR⁴, -NH₂, -NHR⁵, -N(R⁵)₂, C₂-C₂₀ alkenyl, C_rC₂₀ alkoxy, CrC₂₀ alkyl, C₂-C₂₀ alkynyl, Ce-C₂₀ aralkyl, C₆-Ci₂ aryl, C₃-C₈ cycloalkyl, Cr C₂₀ aminoalkyl, CrC₆ hydroxyalkyl, C_rCi₂ heteroaryl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S, and C1-C12 heterocyclyl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S ;

R² and R³ are the same or different and are selected from the group consisting of a -OH, -SH, -OR⁶, -SR⁶, -NH₂, -NHR⁵, -N(R⁵)₂₎ and 0(C=O)R⁴;

R⁴ is a CrC₂₀ alkyl which is linear or branched, C₃-Ci₂ cycloalkyl, Cr Ci₂ heterocyclyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆-Ci₂ aryl, C₆-C₂₀ aralkyl, C₆- C₂₀ alkylaryl, and CrCi₂ heteroaryl;

R⁵ is a CrC₂₀ alkyl which is linear or branched, C₃-Ci₂ cycloalkyl, Cr Ci₂ heterocyclyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆-Ci₂ aryl, C₆-C₂₀ aralkyl, C₆- C₂₀ alkylaryl, CrCi₂ heteroaryl, and a suitable protecting group for an amine; R⁶ is a C1-C₂0 alkyl which is linear or branched, C3-C12 cycloalkyl, Cr C₁₂ heterocyclyl, C₂-C_2O alkenyl, C₂-C₂₀ alkynyl, C₆-Ci₂ aryl, C₆-C₂₀ aralkyl, C₆- C₂₀ alkylaryl, C₁-Ci₂ heteroaryl, and a suitable protecting group for a hydroxy group or a thiol group;

X¹ is an anion selected from the group consisting of F^', Cl^", Br^", I^", (CN)₂N^", BF₄ ^", SbF₆ ^", BH₄ ^", AsF₆ ^", CH₃COO^", CF₃COO^", CH₃SO₃ ^", CF₃SO₃ ^", FSO₃ ^", (FSO₂J₂N^", (C₂F₅SO₂)₂N^", NO₃ ^", N₃ ^", CIO₄ ^" ,TsO^" (tosylate), NsO^" (nosylate), HSO₄ ^2", [MX₄]^", [M₂X ₇]^" (wherein M is a metal such as iron and X is F^", Cl^", Br^", or I ), (CF₃SO₂)₂N^"and PF₆ ^"

X² and X³ are the same or different and each represent an oxygen atom or a sulphur atom;

m is an integer having a value from 1 to 3;

n is an integer having a value from 1 to 3; and

p is an integer having a value from 1 to 12.

It was found that these compounds can be very useful for acting as ionic liquids and ligands. In fact, these compounds, which have ionic liquids properties, can be useful from complexing or chelating metals. They can be used in any applications in which the removal of metals is required. For example, water (or other liquids and/ or fluids) contaminated with metals may be remediated through use of these compounds. They can form complexes with metals so as to obtain specialized catalysts that are soluble in other ionic liquids. By forming complexes with such compounds, it is possible to vary the nature of the metal comprised into the complexe, thereby obtaining catalysts having different properties. Such catalysts can also be recyclable.

According to another aspect of the invention, there is provided a process for preparing a compound of formula (I), as previously defined. The process comprises the step of reacting together compounds of formulas (II), (III), and (IV):

(H) (III) (IV)

wherein L¹ and L² are the same or different and each represent a leaving group. Such a reaction can be carried out in the presence of a base.

According to another aspect of the invention, there is provided a process for preparing a compound of formula (I), as previously defined. The process comprises the step of reacting together compounds of formulas (V) and (Vl):

(V) (VI)

wherein L³ represents a leaving group; and R¹, R², R³, X¹, X², X³, m, n and p are as previously defined. Such a reaction can be carried out in the presence of a base.

It was found that the processes of the present invention permit to simply, efficiently and rapidly prepare the compounds of the present invention. It was also found that such processes can be carried out at low costs and by avoiding tedious tasks.

According to another aspect of the invention, there is provided a metal extraction process comprising the step of complexing the metal with at least one compound of the present invention. By using such a process a metal, can be removed from a composition or solution comprising a solvent and the metal. Such a method can be used for various purposes such as for removing a contaminating metal from a composition, liquid or solution.

According to another aspect of the invention, there is provided a method for at least partially extracting a metal from a composition comprising the metal and a liquid, the method comprising reacting the composition with at least one compound as defined in the present invention so as to form a complex and separating the obtained complex from the rest of the composition.

According to another aspect of the invention, there is provided a method for decontaminating a liquid that is contaminated with a metal, the method comprising the step of extracting the metal by means of a compound as defined in the present invention.

According to another aspect of the invention, there is provided a kit for extracting a metal comprising a compound as defined in the present invention, together with instructions indicating how to use such a compound.

A kit for decontaminating a liquid contaminated with a metal, the kit comprising at least one compound as defined in the present invention, together with instructions indicating how to use such a compound.

It was found that the methods and kits of the present invention are very useful for performing various tasks since the compounds used therewith are efficient for complexing metals.

According to another aspect of the invention, there is provided a complex comprising a metal complexed by at least one compound as those defined in the present invention.

According to another aspect of the invention, there is provided a complex comprising a metal complexed by at least two compounds as those defined in the present invention. These at least two compounds can be same or different.

According to another aspect of the invention, there is provided a complex of formula (VII):

(VII)

wherein R¹⁷ is a positively charged heterocyclic ring, which is unsubstituted or substituted with 1 to 3 substitutents selected from the group consisting of halogen atom, -NO₂, -CN -OH, -CF₃ -COR⁴, -SH, -OMe, -SMe, - SPh, -COOH, -COOR⁴, -NH₂, -NHR⁵, -N(R⁵)₂, C₂-C₂₀ alkenyl, CrC₂₀ alkoxy, Ci-C₂₀ alkyl, C₂-C₂₀ alkynyl, C₆-C₂₀ aralkyl, C₆-Ci₂ aryl, C₃-C₈ cycloalkyl, d- C₂₀ aminoalkyl, CrC₆ hydroxyalkyl, CrCi₂ heteroaryl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S, and CrCi₂ heterocyclyl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S;

R⁴ is a CrC₂₀ alkyl which is linear or branched, C₃-Ci₂ cycloalkyl, d- Ci₂ heterocyclyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆-Ci₂ aryl, C₆-C₂₀ aralkyl, C₆- C₂₀ alkylaryl, and CrCi₂ heteroaryl;

R⁵ is a CrC₂₀ alkyl which is linear or branched, C₃-Ci₂ cycloalkyl, Cr Ci₂ heterocyclyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆-Ci₂ aryl, C₆-C₂₀ aralkyl, C₆- C₂₀ alkylaryl, CrCi₂ heteroaryl, and a suitable protecting group for an amine; X⁴ is an oxygen atom or a sulphur atom;

X⁵ is the same or different and are selected from the group consisting of a -OH, -SH, -OR⁶, -SR⁶, -NH₂, -NHR⁵, -N(R⁵)₂, and -0(C=O)R⁴;

M¹ is a metal selected from the group consisting of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Ac, Th, Pa, U, Np, Pu, Am₁ Cm, Bk, Cf, Es, Fm, Md, No, Lr, Al, Ga, In, Ti, Sn, and Pb;

q is an integer having a value from 1 to 12; and

r is an integer having a value from 1 to 3.

The term "aryl" has used herein refers to a cyclic or polycyclic aromatic ring. For example, the aryl group can be phenyl or napthyl.

The term "heteroaryl" has used herein refers to an aromatic cyclic or fused polycyclic ring system having at least one heteroatom selected from the group consisting of N, O, and S. For example, the heteroaryl groups can include but are not limited to furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, benzofuranyl, benzothiophenyl, carbazolyl, benzoxazolyl, pyrimidinyl, benzimidazolyl, quinoxalinyl, benzothiazolyl, naphthyridinyl, isoxazolyl, isothiazolyl, purinyl, quinazolinyl, among others.

The term "heterocyclyl" includes non-aromatic rings or ring systems that contain at least one ring having at least one hetero atom (such as nitrogen, oxygen or sulfur). For example, this term can include all of the fully saturated and partially unsaturated derivatives of the above mentioned heteroaryl groups. Examples of heterocyclic groups include, without limitation, pyrrolidinyl, tetrahydrofuranyl, morpholinyl, thiomorpholinyl, piperidinyl, piperazjnyl, thiazolidinyl, isothiazolidinyl, and imidazolidinyl.

The expression "suitable protecting group for an amine" refers to a protecting group as defined in Greene et al. in "Protective Groups in Organic Synthesis", 3rd Edition, 1999, 494-653, which is hereby incorporated by reference.

The expression "suitable protecting group for a hydroxy group or a thiol group" refers to a protecting group as defined in Greene et al. in "Protective Groups in Organic Synthesis", 3rd Edition, 1999, 17-292 and 454-493, which is hereby incorporated by reference.

In the compounds of the present invention, R² and R³ can be the same. X² and X³ can also be the same. Moreover, m and n can also have the same value. R¹ can be of formula :

wherein each formula is as presented above or substituted with 1 to 3 substituents as defined for R¹ in claim 1 ;

R⁷ represents a hydrogen atom, halogen atom, -NO₂, -CN -OH, -CF₃ - COR⁴, -SH, -OMe, -SMe, -SPh, -COOH, -COOR⁴, -NH₂, -NHR⁵, -N(R⁵)₂,

C₂-C₂O alkenyl, CrC₂O alkoxy, Ci-C₂₀ alkyl, C₂-C₂₀ alkynyl, C₆-C₂O aralkyl, C₆- Ci₂ aryl, C₃-C₈ cycloalkyl, CrC₂₀ aminoalkyl, Ci-C₆ hydroxyalkyl, C_rCi₂ heteroaryl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S, and C₁-C₁₂ heterocyclyl comprising 1 to 4 heteroatoms selected from the group consisting of N₁ O and S;

R⁸, R⁹, and R¹⁰ are same or different and each independently represent a C₁-C2₀ alkyl which is linear or branched, C3-C12 cycloalkyl, C1-C12 heterocyclyl, C2-C20 alkenyl, C2-C20 alkynyl, C₆-Ci₂ aryl, C₆-C₂O aralkyl, C₆-C₂₀ alkylaryl, C₁-C₁₂ heteroaryl, and a suitable protecting group for an amine;

R¹¹, R¹², and R¹³ are same or different and each independently represent a Ci-C_2O alkyl which is linear or branched, C₃-Ci₂ cycloalkyl, Ci-C-ι₂ heterocyclyl, C₂-C₂O alkenyl, C2-C20 alkynyl, C₆-Ci₂ aryl, C₆-C₂₀ aralkyl, C₆-C₂₀ alkylaryl, Ci-Ci₂ heteroaryl, and a suitable protecting group for a phosphorus atom;

R¹⁴ and R¹⁵ are same or different and each independently represent a CrC₂₀ alkyl which is linear or branched, C₃-Ci₂ cycloalkyl, CrCi₂ heterocyclyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆-Ci₂ aryl, C₆-C₂₀ aralkyl, C₆-C₂₀ alkylaryl, CrCi₂ heteroaryl, and a suitable protecting group for a sulphur atom; and

R⁴, R⁵, R⁶ and X₂ is as previously defined in claim 1.

For example, R¹ can be of formula

wherein R¹⁶ is a C1-C₄ alkyl group. Methyl and butyl are non-limitative examples of such alkyl groups. R¹⁶ can alternatively be a C₁-C1₂ alkyl group. Butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl are also non-limitative examples. R1 can alternatively be a nitrogen-containing charged heterocyclic ring (such as imidazolium, pyridinium, pyrrolidinium, pyrimidinium, pyrazinium, or indolium).

In the compounds of the present invention, R² and R³ can be the same and they can each represent -OH or -OR⁶, wherein R⁶ is a C1-C8 linear or branched alkyl group. X² and X³ can be the same and they can each represent an oxygen atom. X¹ is for example selected from the group consisting of halides F-, Cl-, Br-, I-, (CN)₂N-, BF₄-, (CF₃SO₂)2N- and PF₆-. Alternatively, X¹ can be PF₆-.

In the compounds of the present invention, m and n can have, for example, a value of 1. p can have , for example, a value of 1 to 3. p can also have, for example, a value of 2 or 3.

The compounds of the present invention can be used for complexing a cation. The cation can be a cation of a metal selected from the group consisting of Li, Na, K, Rb, Cs, Fr, Be₁ Mg, Ca, Sr, Ba, Ra, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt₁ Au, Hg, Ac, Th, Pa₁ U₁ Np₁ Pu₁ Am₁ Cm₁ Bk₁ Cf₁ Es, Fm₁ Md₁ No, Lr, Al₁ Ga₁ In, Ti, Sn, and Pb. The cation can be a bivalent cation. The cation can be selected from the group consisting of Cu²⁺, Ni²⁺, and Co²⁺. The compounds of the present invention can also be used in a metal extraction process, for purifying air, for decontaminating a liquid by extracting a metal present in the liquid with the compound, or as an ionic liquid.

In the processes of the present invention, compounds of formulas (III) and (IV) can be identical. L1 can be selected from the group consisting of Cl, Br, I₁ tosylate, mesylate, brosylate, and OH2. L2 can be selected from the group consisting of Cl, Br, I, tosylate, mesylate, brosylate, and OH2. L3 can be selected from the group consisting of Cl, Br, I, tosylate, mesylate, brosylate, and OH2. Alternatively, L¹, L², and L³, can be Cl- or Br-.

- ii - In the methods and kits of the present invention, the step of extracting can comprise reacting the compound as previously defined, together with the metal so as to form a complex and then, separating the complex from the liquid. The cation can be a cation of a metal selected from the group consisting of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y₁ Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr, Al, Ga, In, Ti, Sn, and Pb. For example, the metal can be a bivalent cation. The metal can be selected from the group consisting of Cu²⁺, Ni²⁺, and Co²⁺.

The complexes of the present invention can comprise two compounds as previously defined. These compounds can be identical. M1 or the metal complexed by such compound(s) can be selected from the group consisting of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Ac, Th₁ Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md₁ No₁ Lr₁ Al₁ Ga₁ In₁ Ti, Sn, and Pb. M1 can be a bivalent cation. M1 can be, for example, selected from the group consisting of Cu²⁺, Ni²⁺, and Co²⁺.

In the complexes of the present invention, R 17 can be of formula

wherein each formula is as presented above or substituted with 1 to 3 substituents as defined for R¹⁷ in claim 46;

R⁷ represents a hydrogen atom, halogen atom, -NO₂, -CN -OH, -CF₃ - COR⁴, -SH, -OMe, -SMe₁ -SPh, -COOH, -COOR⁴, -NH₂, -HR⁵, -N(R⁵)₂,

C₂-C₂₀ alkenyl, C₁-C₂₀ alkoxy, CrC₂₀ alkyl, C₂-C₂₀ alkynyl, C₆-C₂₀ aralkyl, C₆- Ci₂ aryl, C₃-Ce cycloalkyl, Ci-C₂₀ aminoalkyl, CrC₆ hydroxyalkyl, CrCi₂ heteroaryl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S, and CrCi₂ heterocyclyl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S;

R⁸, R⁹, and R¹⁰ are same or different and each independently represent a CrC₂₀ alkyl which is linear or branched, C₃-Ci₂ cycloalkyl, CrCi₂ heterocyclyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆-Ci₂ aryl, C₆-C₂₀ aralkyl, C₆-C₂₀ alkylaryl, CrCi₂ heteroaryl, and a suitable protecting group for an amine;

R¹¹, R¹², and R¹³ are same or different and each independently represent a CrC₂₀ alkyl which is linear or branched, C₃-Ci₂ cycloalkyl, CrCi₂ heterocyclyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆-Ci₂ aryl, C₆-C₂₀ aralkyl, C₆-C₂₀ alkylaryl, CrC₁₂ heteroaryl, and a suitable protecting group for a phosphorus atom;

R⁴, R⁵ and X₂ is as previously defined in claim 46.

For example, R¹⁷ can be of formula :

wherein R¹⁶ is a CrC₄ alkyl group. R¹⁶ can be, for example, methyl or butyl. R¹⁶ can alternatively be a C₁-C₁₂ alkyl group. Butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl are also non-limitative examples.

R¹⁷ can alternatively be a nitrogen-containing charged heterocyclic ring (such as imidazolium, pyridinium, pyrrolidinium, pyrimidinium, pyrazinium, or indolium).

In the complexes of the present invention, X⁴ can be an oxygen atom. X⁵ can also be an oxygen atom, r can have a value of 1. q can have a value of 2 or 3.

The complexes of the present invention can be used for purifying air or for removing metal contaminants from impure liquids such as water, factory effluent, and petroleum products.

The compounds, complexes and methods of the present invention also permit the quantification of the efficiency of the chelating ionic liquids for their ability. They also permit the partition of metals in to the organic phase (ICP-MS). It is also possible, for the compounds and complexes of the present invention, to evaluate the efficiency of ionic liquids for remediation of the metals ions on the environmental blacklist. These compounds and complexes can be reusable and they can be used as catalysts.

BRIEF DESCRIPTION OF FIGURES

Further features and advantages of the invention will become more readily apparent from the following description of specific embodiments as illustrated by way of examples in the appended figures wherein:

Fig. 1 shows a X-ray crystal of a complex according to one embodiment of the invention, wherein the complex if of formula 6a; and Fig. 2 represents a picture comparing the water solubility of various complexes according to various specific embodiments of the present invention, said complexes being of formulas 15b, 15c, 15d, and 15e.

DETAILED DESCRIPTION OF THE INVENTION

The following non-limiting examples further illustrate the invention.

Some compounds of the present invention have been prepared according to a specific embodiment of the invention, which is illustrated in Scheme 1.

Scheme 1 :

(Vj

6a : M = Cu 6b : M = Ni 6c : M = Co The reagents and conditions used in Scheme 1 are as follows: (i) 2- ethanolamine (lequiv.), rt, then 100 ⁰C, 1.25 h, cooled to rt, then PBr₃ (0.68 equiv.) at rt, then 100 ⁰C, 1.25 h ; (ii) 1-methylimidazole (1.1 equiv.), toluene, 70 ⁰C, 48 h; (iii) HPF₆ (1.2 equiv., 60 w% aq.), rt; (iv) ethylenediamine (8 equiv.), 1-butanol at rt, then 90 ⁰C, 24 h; (v) diisopropylethylamine (2 equiv.), NaI (0.55 equiv.), THF at rt, then 67 ⁰C, 1 h, cooled to rt, then tert- butylbromoacetate (2 equiv.), 67 ⁰C, 24 h; (vi) CF3COOH (100 equiv., 50 v% in CH₂CI₂), rt for 24 h, then evaporation under reduced pressure, then MCI₂. xH₂O (0.5 equiv.) (aq.), then NH₃ (aq., 25%).

The most common amino group protected α,ω-haloamine is N-(2- bromoethyl)phthalimide 1 , which was prepared by one-pot, two step procedure using the condensation of 2-aminoethanol with phthalic anhydride and the subsequent bromination with PBr₃. 1-Methylimidazole was then subjected to the quaterisation reaction with N-(2-bromoethyl)phthalimide 1 , to result in the formation of the quaternary bromide 2 in 40% yields. The quaternary bromide 2, being water soluble, was subjected to the anion exchange reaction (metathesis) with the aqueous solution of HPF6, resulting in the formation of 3, the imidazolium salt with the phthaloyl group on the side chain and PF₆- as the counter anion. The yield of the product in this step was 98%. The hexafluorophosphate salt, 3 was subjected to the deprotection of phthaloyl group with ethylenediamine in 1-butanol at 90 ^CC for 24 h, to result in the formation of the imidazolium salt with the amino group in side chain, namely 1-(2'-aminoethyl)-3-methylimidazolium hexafluorophosphate 4, in 93% yield. The amino functionalized imidazolium salt 4 was then subjected to base promoted N,N-dialkylation using two equivalents of tert-butylbromoacetate. The isolation of the product in the fifth step, to get pure diester 5, required the use of the column chromatography. A 4% MeOH in CH₂CI₂ was used as an eluent for the purpose of this embodiment.

The characterization of the compounds from 1 to 5 was mainly by the NMR tools. The existence of the cations in all these compounds was ascertained by the 1 H, 13C NMR and ESI MS. The anionic part in these compounds was confirmed by the ESI MS and also by 31 P and 19F NMR spectra wherever necessary. The overall yield of the synthetic sequence from (ii) to (v) is 13%. The steps from (i) to (iv) did not require any complex purification procedures to isolate the pure product.

Synthesis of 1

The synthetic procedure leading to 1 is adopted from the Organic Synthesis, coll. Vol. 1 , p 119. The product is characterized as follows : Melting point: 80-82 ⁰C

IR (KBr): 3091 , 3048, 2947, 2911 , 1698, 1607, 1465, 1431 , 1391 , 1225, 1166, 1067, 973, 922, 861 , 803, 721 , 599, 506 cm-1

1H NMR (250 MHz, CDCI₃): δ 3.59-3.65 (t, J = 6.8 Hz, 2H, -CH₂-CH₂-Br), 4.09-4.14(t, J = 6.6 Hz, 2H, -CH₂-CH₂-Br), 7.73-7.78 (m, 2H, 2 x CH arom.), 7.86-7.90 (m, 2H, 2 * CH arom.) ppm

13C NMR (63 MHz, CDCI₃): δ 28.14, 39.31 , 123.51 , 131.86, 134.22, 167.80 ppm.

Synthesis of 2

To a solution of N-(2-bromoethyl)phthalimide 1(57.7 g, 227 mmol) in toluene (200 ml_) is added 1-methylimidazole (20.5 g, 19.9 mL, 250 mmol) under nitrogen atmosphere, the resulting solution is heated at 70 ⁰C for 48 h with constant stirring in inert atmosphere. The quaterisation product is toluene insoluble and precipitates as white solid as the reaction proceeds. The reaction work up involves cooling of the reaction mixture to room temperature and filtering the product. The product is washed with cold toluene. Subsequently, the crystals are dried. The yield of the reaction is 30.5 g (40% of the theory). The product 1-(2'-phthalamidoethyl)-3-methylimidazolium bromide 2 is characterized as follows:

Melting point: 182-184 ⁰C

IR (KBr): 3151 , 3109, 1770, 1714, 1609, 1569, 1464, 1431 , 1401 , 1322, 1169, 1128, 1085, 1003, 760, 721 , 604, 524 cm-1

1 H NMR (250 MHz, D2O): δ 3.89 (s, 3H, N-CH3), 4.14^.18 (m, 2H, Pht- CH2-CH2-lm), 4.52-4.57 (m, 2H, Pht-CH2-CH2-lm), 7.44-7.45 (m, 1 H, 1 x CH arom.), 7.54-7.56 (m, 1 H₁ 1 x CH arom.), 7.86 (s, 4H, 4 x CH arom.), 8.84 (s, 1 H, 1 x CH arom.) ppm.

13C NMR (63 MHz, D2O): δ 36.17, 38.24, 48.22, 123.01, 123.88, 124.19, 130.98, 135.36, 136.72, 169.87 ppm

ESI MS: In positive mode peaks at m/z 257.0, 256.0 and 174.0 a.m.u. and in negative mode peak at m/z 78.9 and 80.9 a.m.u.

Synthesis of 3

To the solution of 1-(2'-phthalamidoethyl)-3-methylimidazolium bromide 2 (30.7 g, 90.7 mmol) in water (500 ml_) is added HPF₆ (26.5 ml_ of 60 w % solution, 109 mmol) in cold conditions over 1 hr. The precipitation of the white solid occurs as the addition of aq. HPF₆ goes on. After the addition is complete, the reaction mixture is stirring further at room temperature for 0.5 h. The reaction workup involves filtration of the product under suction and subsequently drying in to obtain the dry white powder. The yield of the reaction is 35.9 g (98% of the theory). The product, 1-(2'-phthalamidoethyl)-3- methylimidazolium hexafluorophosphate 3 is characterized as follows :

Melting point: 194-196 ⁰C

IR (KBr): 3171 , 1773, 1714, 1618, 1585, 1465, 1411 , 1329, 1170, 1135, 1088, 1033, 1008, 825, 753, 722, 655, 623, 558, 528 cnrT¹

¹H NMR (250 MHz, acetone cf_β): δ 4.03 (s, 3H, N-CH₃), 4.20-4.24 (t, J = 5.3 Hz, 2H, PW-CH₂-CH₂-Im), 4.68^.72 (t, J = 5.1 Hz, 2H, Pm-CH₂-CH₂-Im), 7.70 (s, 1 H, 1 x CH arom.), 7.86 (s, 5H, 5 x CH arom.), 9.11 (s, 1H₁ 1 x CH arom.) ppm.

¹³C NMR (63 MHz, DMSO Cf₆): δ 35.74, 37.98, 47.84, 122.87, 123.21 , 123.57, 131.52, 134.51 , 137.11 , 167.64 ppm

ESI MS: In positive mode peaks at m/z 257.0, 256.0 and 174.0 a.m.u. and in negative mode peak at m/z 144.7 a.m.u.

³¹P NMR (101 MHz, acetone d₆): -159.55 to -117.66 ppm (septet) ¹⁹F NMR (235 MHz, acetone d₆): -69.73 to -66.73 ppm (doublet) Synthesis of 4

To the suspension of 1-(2'-phthalamidoethyl)-3-methylimidazolium hexafluorophosphate 3 (10.02 g, 25 mmol) in 1-butanol (200 ml_), is gradually added ethylenediamine (12 g, 13.40 ml_, 200 mmol) over 15 min at room temperature. The resulting solution is heated at 90 ⁰C for 24 h, while it is continuously stirred. The product isolation is carried out by cooling the reaction mixture to room temperature and isolating the white insoluble mass by filtration and subsequent washing it with cold butanol. The white solid so obtained is characterized to be the desired product 4. The procedure yields 6.31 g (93% of the theory) of the product. The product, 1-(2'-aminoethyl)-3- methylimidazolium hexafluorophosphate 4 is characterized as follows:

IR (KBr): 3266, 3172, 1642, 1573, 1456, 1336, 1302, 1237, 1173, 1092, 837, 748, 652, 624, 559 cm^"1

¹H NMR (250 MHz, DMSO d_β): δ 1.80 (br s, 2H, -CH₂-CH₂-NH₂), 2.87-2.92 (t, J = 5.8 Hz, 2H, -CH₂-CH₂-NH₂), 3.84 (s, 3H, N-CH₃), 4.07^.11 (t, J = 5.5 Hz, 2H, -CH₂-CH₂-NH₂), 7.67 (s, 1 H₁ 1 x CH arom.), 7.70 (s, 1 H, 1 * CH arom.), 9.04 (s, 1 H, 1 x CH arom.) ppm.

¹³C NMR (63 MHz, DMSO d₆): δ 35.62, 41.24, 51.99, 122.49, 123.27, 136.71 ppm.

ESI MS: In positive mode peaks at m/z 170.0, 127.1 , 126.1 and 83.2 a.m.u. and in negative mode peak at m/z 144.7 a.m.u.

³¹P NMR (101 MHz, DMSO d₆): -159.99 to -117.92 ppm (septet). ¹⁹F NMR (235 MHz, DMSO cf_β): -67.88 to -64.86 ppm (doublet).

Synthesis of 5

To the solution of 1-(2'-aminoethyl)-3-methylimidazolium hexafluorophosphate 4 (5.0 g, 18.5 mmol) in dry THF (100 ml_), is added sodium iodide (1.53 g, 10.2 mmol) and diisopropylethylamine (4.77 g, 6.43 ml_, 37 mmol) at room temperature and the mixture is then refluxed at 67 ⁰C for 1 h with constant stirring. The solution is allowed to be cold again to the room temperature and tert-butylbromoaceate (7.22 g, 5.47 ml_, 37 mmol) is added to it dropwise with stirring. After the addition of tert-butylbromoaceate is completed, the solution is refluxed again at 67 ⁰C for 24 h, while the reaction mixture is constantly stirred. The reaction workup involves evaporation of THF under reduced pressure followed by the column chromatography, to fetch the pure product. The yield of the product so obtained after column chromatography is 3.32 g (36% of the theory). The product 5 is characterized as follows:

Melting point: 90-92 ⁰C

IR (KBr): 3155, 3081, 2980, 2930, 1732, 1567, 1458, 1369, 1233, 1161, 1064, 999, 971, 834, 747, 654, 624, 558 cm^'1

¹H NMR (250 MHz, CDCI₃): δ 1.44 (s, 18H, 6 * -CH₃), 3.11-3.13 (m, 2H, - CH₂-CH₂-N(CH₂COOB^)₂), 3.36 (s, 4H, -CH₂-CH₂-N(CH₂COOB^)₂), 3.92 (s, 3H, N-CH₃), 4.16-4.18 (m, 2H, -CH₂-CH₂-N(CH₂COOBU^t)₂), 7.20-7.21 (m, 1 H, 1 x CH arom.), 7.61-7.62 (m, 1H₁ 1 x CH arom.), 8.99 (s, 1H₁ 1 x CH arom.) ppm.

¹³C NMR (63 MHz, CDCI₃): δ 28.09, 36.11 , 48.20, 54.66, 56.69, 81.73, 122.42, 123.30, 137.31 , 170.58 ppm

ESI MS: In positive mode peak at m/z 355.2 and 354.2 a.m.u. and in negative mode peak at m/z 144.7 a.m.u.

³¹P NMR (101 MHz, CDCI₃): -164.97 to -122.83 ppm (septet). ¹⁹F NMR (235 MHz, CDCI₃): -74.87 to -71.85 ppm (doublet). Synthesis of metal complexes 6a, 6b, and 6c

To the solution of 5 (0.20Og, 0.401 mmol) in DCM (3 ml_), is added trifluoroacetic acid (3.09 ml_, 4.57 g, 40 mmol), drop wise, at room temperature over 15 min. The resulting solution is stirred at room temperature for 24 h. The solution is evaporated under reduced pressure to yield a syrupy mass. To this is added the aqueous solution of metal halide (MCI₂) (0.200 mmol in 10 ml_) and the resulting mixture is stirred and basified slowly with aqueous NH3 (25%), till the solution reaches pH 10. The complexes (M²⁺ is Cu²⁺ (6a), Ni²⁺ (6b) and Co²⁺ (6c)) are water soluble and are obtained as crystals from water by slow evaporation of their saturated solutions. Complexes 6a, 6b and 6c are characterized as follows: Copper complex 6a

IR (Nujol): 3508, 3363, 3284, 3159, 3086, 1676, 1633, 1562, 1461 , 1399, 1369, 1321 , 1295, 1261 , 1227, 1179, 1119, 1039, 993, 967, 896, 862, 772, 744, 722, 666, 629, 555, 530 cm ¹.

ESI MS: In positive mode peaks at m/z 543.9, 566.0, 499.0, 413.1, 326.0, 264.0, 242.0, 160.0 and 81.1 a.m.u. and in negative mode no peak observed.

The X-ray crystal structure is shown in Fig. 1.

Selected interatomic distances (A) and angles (°): Cu-O(I) 1.936(1), Cu-O(3) 2.382(1), Cu-N(I) 2.064(1), O(5)-O(3) 2.815(x), O(1)-Cu-O(1)i 180.0, O(3)- Cu-O(3)i 180.0, N(1)-Cu-N(1)i 180.0, O(1)-Cu-O(3) 88.3(1), O(1)-Cu-N(1) 86.5(1), O(3)-Cu-N(1) 76.3(1). Symmetry operator: i: -x, -y, -z+1.

Nickel complex 6b

IR (Nujol): 3557, 3495, 3278, 3163, 3104, 3073, 1712, 1661 , 1620, 1588, 1462, 1401 , 1373, 1346, 1313, 1302, 1255, 1222, 1176, 1123, 1095, 1041 , 992, 967, 941 , 917, 895, 845, 770, 730, 668, 626, 579, 543 cm ¹.

ESI MS: In positive mode peaks at m/z 538.9, 561.0, 465.2, 333.2, 289.1 , 242.0 and 160.1 a.m.u. and in negative mode peaks at m/z 536.8, 492.9 and 239.8 a.m.u.

Cobalt complex 6c

IR (Nujol): 3163, 1771 , 1705, 1672, 1372, 1313, 1255, 1222, 1178, 1125, 1094, 1040, 993, 967, 940, 893, 843, 770, 728, 667, 627, 536 cm^"1.

ESI MS: In positive mode peaks at m/z 539.9, 562.0, 495.1 , 421.2, 377.2, 333.2, 242.0, 196.1 and 160.0 a.m.u. and in negative mode peaks at m/z 537.8, 497.1 , 397.0, 283.0 and 239.8 a.m.u.

Other compounds similar to those represented in Scheme 1 have also been prepared according to the same general procedure. These compounds have been prepared as illustrated in Scheme 2. The compounds prepared in accordance to the process illustrated in Scheme 2 have been made by varying the length of the chains connected to the nitrogen atoms of the imidazolium group (see complexes 6a to 6c and 15a1 to 15e). Scheme 2

11a: n = 1 , R₂ = C₄H₉ 12a: n = 1 , R₂ = C₄H₉ 11b: n = 2, R₂ = C₄H₉ 12b: n = 2, R₂ = C₄H₉ + RaBr 11c: n = 2, R₂ = C₆Hi₃ 12c: n = 2, R₂ = C₆H₁₃ 11d: n = 2, R₂ = C₈H₁₇ 12d: n = 2, R₂ = C₈H₁₇

11e: n = 2, R₂ = Ci₀H₂₁ 12e: n = 2, R₂ = Ci₀H₂₁

(ix)

M = Cu M = Ni M = Co = Cu = Cu

= Cu 15e: n = 2, R₂ = C₁₀H₂₁, M = Cu The reagents and conditions used in Scheme 2 are as follows: (vii) Toluene, 70 ⁰C, 48 h; (viii) HPF₆ (1.2 equiv., 60 w%, aq.), rt, 30 min. (ix) hydrazine hydrate (2 equiv.), ethanol, 76 ⁰C, 4 h; (x) diisopropylethylamine (2 equiv.), NaI (0.55 equiv.), THF, rt, then 67 ⁰C, 1 h, cooled to rt, then tert- butylbromoacetate (2 equiv.), 67 ⁰C, 24 h; (xi) CF₃COOH (100 equiv., 50 v% in CH₂CI₂), rt, 24 h, then evaporation at reduced pressure, then MCI₂. xH₂O (0.5 equiv., aq.), then NH₃ (25%, aq.).

Compounds 11a, 11b, 11c, 11d, 11e, 12a, 12b, 12c, 12d, 12e, 13a, 13b, 13c, 13d, 13e, 14a, 14b, 14c, 14d, 14e, 1Sa₁, 15a₂, 15a₃, 15b, 15c, 15d, and 15e which have been prepared according to the same general procedure as previously described have been characterized as follows.

Characterization of 11a Melting point: 96-98 ⁰C

IR (KBr): 3143, 3093, 2966, 2940, 2880, 1770, 1714, 1626, 1563, 1449, 1428, 1392, 1360, 1231 , 1190, 1162, 1120, 1086, 1044, 1006, 930, 883, 841 , 805, 776, 723, 676, 653, 605, 528 cm^"1

¹H NMR (250 MHz, D₂O): δ 0.82-0.88 (t, J = 7.3 Hz, 3H, ImN-(CHz)₃-CH₃), 1.09-1.24 (m, 2H, ImN-(CHz)₂-CH₂-CH₃), 1.71-1.83 (m, 2H, ImN-CH₂-CH₂- CH₂-CH₃), 4.16-^.22 (m, 4H, PMN-CH₂-CH₂-NIm and lmN-CH₂-(CH₂)₂-CH₃), 4.56-4.61 (t, J = 5.5 Hz, 2H, PhtN-CH₂-CH₂-Nlm), 7.54-7.56 (m, 1H, 1 x CH arom.), 7.64-7.66 (m, 1 H, 1 * CH arom.), 7.88 (s, 4H, 4 x CH arom.), 8.89 (s, 1 H, 1 x CH arom.) ppm.

¹³C NMR (63 MHz, D₂O): δ 12.93, 18.82, 31.53, 38.21 , 48.28, 49.74, 123.14, 123.23, 123.92, 130.87, 135.48, 135.96, 169.67 ppm

ESI MS: In positive mode peaks at m/z 299.1 and 298.1 a.m.u. and in negative mode peak at m/z 78.9 and 80.8 a.m.u. Characterization of 11b

IR (KBr) 3158, 3129, 3052, 2951 , 2873, 1779, 1766, 1706, 1610, 1565, 1462, 1433, 1413, 1387, 1349, 1285, 1252, 1238, 1215, 1191 , 1171 , 1140, 1120, 1109, 1090, 1071, 1041 , 971 crrT¹

¹H NMR (250 MHz, DMSO d₆): δ 0.88-0.94 (t, J = 7.4 Hz, 3H, lmN-(CH₂)₃- CH₃), 1.20-1.35 (m, 2H, lmN-(CH₂)2-CH2-CH₃), 1.72-1.83 (m, 2H, ImN-CH₂- CH₂-CH₂-CH₃), 2.13-2.24 (m, 2H, ImN-CH₂-CH₂-CH₂-NPrIt), 3.59-3.65 (t, J = 6.4 Hz, 2H, ImN-CH₂-CH₂-CH₂-CH₃), 4.15^.20 (t, J = 7.1 Hz, 2H, ImN-CH₂- CH₂-CH₂-NPht), 4.22-4.28 (t, J = 7.4 Hz, 2H₁ ImN-CH₂-CH₂-CH₂-NPhIt), 7.81- 7.82 (m, 2H, 2 * CH arom.), 7.83-7.91 (m, 4H, 4 x CH arom.), 9.21 (s, 1 H, 1 x CH arom.) ppm.

¹³C NMR (63 MHz, DMSO d₆): δ 13.25, 18.71 , 28.48, 31.26, 34.29, 46.54, 48.53, 122.34, 122.41 , 122.98, 131.63, 134.37, 136.16, 167.94 ppm

ESI MS: In positive mode peaks at m/z 312.1 and 313.1 a.m.u. and in negative mode peak at m/z 78.9 and 80.9 a.m.u.

Characterization of 11c

IR (KBr) 3162, 3130, 3051 , 2954, 2928, 2871 , 2856, 1779, 1766, 1712, 1610, 1565, 1463, 1433, 1413, 1387, 1348, 1311 , 1284, 1254, 1237, 1191 , 1171 , 1140, 1108, 1090, 1073, 1041 , 971 cm^"1

¹H NMR (250 MHz, DMSO d₆): δ 0.83-0.89 (t, J = 6.8 Hz, 3H, lmN-(CH₂)₅- CH₃), 1.27 (bs, 6H, ImN-CH₂-CH₂-CH₂-CH₂-CH₂-CH₃), 1.73-1.84 (m, 2H, ImN-CH₂-CH₂-(CH₂)_S-CH₃), 2.13-2.24 (m, 2H, ImN-CH₂-CH₂-CH₂-NPm), 3.59-3.64 (t, J = 6.4 Hz, 2H, Im N-CH₂-(CHz)₄-C H₃), 4.14-4.20 (t, J = 7.3 Hz, 2H, ImN-CH₂-CH₂-CH₂-NPW), 4.22^.28 (t, J = 7.3 Hz, 2H, ImN-CH₂-CH₂- CH₂-NPhIt), 7.81-7.82 (m, 2H, 2 * CH arom.), 7.83-7.91 (m, 4H, 4 * CH arom.), 9.21 (s, 1 H, 1 x CH arom.) ppm. ¹³C NMR (63 MHz, D₂O): δ 13.54, 22.07, 25.28, 28.14, 29.40, 30.61 , 34.81 , 47.36, 49.95, 122.52, 122.88, 123.55, 131.09, 135.15, 135.72, 170.14 ppm

ESI MS: In positive mode peaks at m/z 340.2 and 341.2 a.m.u. and in negative mode peak at m/z 79.0 and 80.9 a.m.u.

Characterization of 11d

IR (KBr): 3160, 3130, 3053, 2954, 2924, 2854, 1779, 1766, 1712, 1611 , 1564, 1464, 1433, 1413, 1387, 1348, 1311 , 1284, 1253, 1238, 1190, 1174, 1140, 1108, 1090, 1073, 1041 , 971 cm^"1

¹H NMR (250 MHz, DMSO d₆): δ 0.82-0.87 (t, J = 6.3 Hz, 3H, lmN-(CH₂)₇- CH₃), 1.25 (bs, 10H, ImN-(CHz)₂-CH₂-CH₂-CHrCH₂-CH₂-CH₃), 1.73-1.84 (m, 2H, ImN-CH₂-CH₂-(CH₂)S-CH₃), 2.13-2.24 (m, 2H, ImN-CH₂-CH₂-CH₂-NPlIt), 3.59-3.64 (t, J = 6.4 Hz, 2H, ImN-CH₂-(CH₂)_S-CH₃), 4.13-4.18 (t, J = 7.3 Hz, 2H, ImN-CH₂-CH₂-CH₂-NPlIt), 4.21-4.27 (t, J = 7.3 Hz, 2H, ImN-CH₂-CH₂- CH₂-NPlIt), 7.79-7.80 (m, 2H, 2 x CH arom.), 7.83-7.91 (m, 4H, 4 x CH arom.), 9.18 (s, 1 H, 1 * CH arom.) ppm.

¹³C NMR (63 MHz, DMSO d₆): δ 13.89, 22.04, 25.45, 28.33, 28.47, 28.58, 29.34, 31.13, 34.28, 46.53, 48.79, 122.35, 122.45, 122.99, 131.62, 134.40, 136.19, 167.95 ppm

ESI MS: In positive mode peaks at m/z 368.2 and 369.2 a.m.u. and in negative mode peak at m/z 79.0 and 80.9 a.m.u.

Characterization of 11e

IR (KBr): 3158, 3131 , 3054, 2954, 2919, 2852, 1766, 1712, 1611 , 1566, 1464, 1433, 1413, 1387, 1348, 1284, 1238, 1190, 1173, 1141 , 1109, 1090, 1073, 1041 , 971 cm^"1 ¹H NMR (250 MHz, DMSO d₆): δ 0.81-0.86 (t, J = 6.5 Hz, 3H, lmN-(CH₂)₉- CH₃), 1.23 (bs, 14H, lmN-(CH₂)2-C H ^CH₂-CH₂-C H ^C H ^₂-C H '2-CH₂-CH₃), 1.73-1.84 (m, 2H, ImN-CHz-CHHCH^-CHs), 2.13-2.24 (m, 2H, ImN-CH₂- CH₂-CH₂-NPM), 3.59-3.64 (t, J = 6.4 Hz, 2H, ImN-CH₂-(CH₂)S-CH₃), 4.13- 4.19 (t, J = 7.0 Hz, 2H, ImN-CH₂-CH₂-CH₂-NPlIt), 4.22-4.28 (t, J = 7.3 Hz, 2H, ImN-CH₂-CH₂-CH₂-NPlIt), 7.80-7.81 (m, 2H, 2 x CH arom.), 7.83-7.91 (m, 4H, 4 x CH arom.), 9.20 (s, 1 H, 1 x CH arom.) ppm.

¹³C NMR (63 MHz, DMSO d₆): δ 13.83, 21.99, 25.39, 28.30, 28.50, 28.58, 28.74, 28.79, 29.25, 31.18, 34.24, 46.51 , 48.78, 122.31 , 122.40, 122.95, 131.61 , 134.35, 136.15, 167.89 ppm

ESI MS: In positive mode peaks at m/z 396.3 and 397.1 a.m.u. and in negative mode peak at m/z 79.1 and 81.0 a.m.u.

Characterization of 12a Melting point: 127-129⁰C

IR (KBr): 3153, 3099, 2968, 2936, 2877, 1776, 1712, 1617, 1569, 1466, 1427, 1399, 1365, 1170, 1124, 1088, 1049, 1011 , 935, 842, 756, 722, 649, 609, 558, 530 cm^"1

¹H NMR (250 MHz, DMSO c/₆): δ 0.80-0.86 (t, J = 7.4 Hz, 3H, lmN-(CH₂)₃- CH₃), 1.08-1.23 (m, 2H, ImN-(CH₂)^CH₂-CH₃), 1.62-1.73 (m, 2H, ImN-CH₂- CH₂-CH₂-CH₃), 3.99-4.04 (t, J = 5.3 Hz, 2H, PWN-CH₂-CH₂-NIm), 4.08-4.14 (t, J = 6.8 Hz, 2H₁ ImN-CH₂-(CHz)₂-CH₃), 4.40-4.45 (t, J = 5.3 Hz, 2H, PhtN- CH₂-CH₂-NIm), 7.74-7.75 (m, 1 H, 1 x CH arom.), 7.85-7.88 (m, 5H, 5 x CH arom.), 9.23 (s, 1 H, 1 x CH arom.) ppm.

¹³C NMR (63 MHz, DMSO d₆): δ 13.18, 18.41 , 31.28, 37.96, 47.99, 48.53, 122.55, 123.02, 123.14, 131.46, 134.52, 136.50, 167.56 ppm ESI MS: In positive mode peaks at m/z 299.1 and 298.1 a.m.u. and in negative mode peak at m/z 144.7 a.m.u.

³¹P NMR (101 MHz, acetone d_β): -159.95 to -117.88 ppm (septet)

¹⁹F NMR (235 MHz, acetone d₆): -67.90 to -64.88 ppm (doublet)

Characterization of 12b Melting point: 85-87 ⁰C

IR (KBr) 3163, 3123, 2966, 2880, 1770, 1717, 1615, 1568, 1468, 1443, 1410, 1387, 1343, 1289, 1223, 1192, 1170, 1144, 1112, 1090, 1073, 1043, 968 cm ¹

¹H NMR (250 MHz, DMSO d_β): δ 0.89-0.94 (t, J = 7.4 Hz, 3H, lmN-(CH₂)₃- CH₃), 1.21-1.36 (m, 2H, ImN-(CHz)₂-CH₂-CH₃), 1.73-1.84 (m, 2H, ImN-CH₂- CH₂-CH₂-CH₃), 2.14-2.25 (m, 2H, ImN-CH₂-CH₂-CH₂-NPlIt), 3.61-3.66 (t, J = 6.4 Hz, 2H, ImN-CH₂-CH₂-CH₂-CH₃), 4.14^.20 (t, 2H, J = 7.3 Hz, ImN-CH₂- CH₂-CH₂-NPW), 4.22-4.28 (t, 2H, J = 7.4 Hz, ImN-CH₂-CH₂-CH₂-NPrIt), 7.78- 7.80 (m, 2H, 2 * CH arom.), 7.83-7.91 (m, 4H, 4 x CH arom.), 9.15 (s, 1 H, 1 x CH arom.) ppm.

¹³C NMR (63 MHz, CD₃CN): δ 13.72, 20.04, 29.81 , 32.51 , 35.33, 48.26, 50.48, 123.53, 123.58, 124.01 , 133.17, 135.39, 136.57, 169.54 ppm

ESI MS: In positive mode peaks at m/z 312.1 and 313.1 a.m.u. and in negative mode peak at m/z 144.7 a.m.u.

³¹P NMR (101 MHz, DMSO d₆): -159.89 to -117.92 ppm (septet)

¹⁹F NMR (235 MHz, DMSO d_β): -67.92 to -64.90 ppm (doublet) Characterization of 12c Melting point: 78-80 ⁰C

IR (KBr) 3163, 3122, 2957, 2936, 2862, 1862, 1770, 1718, 1614, 1568, 1468, 1439, 1412, 1387, 1346, 1307, 1289, 1237, 1221 , 1192, 1171 , 1142, 1111 , 1090, 1073, 1044, 970 cm^"1

¹H NMR (250 MHz, DMSO d₆): δ 0.84-0.89 (t, J = 6.6 Hz, 3H, lmN-(CH₂)₅- CH₃), 1.27 (bs, 6H, ImN-CH₂-CH₂-CH₂-CH₂-CH₂-CH₃), 1.74-1.85 (m, 2H, ImN-CH₂-CH₂-(CH₂)_S-CH₃), 2.14-2.25 (m, 2H, lmN-CH₂-CH₂-CH₂-NPht), 3.60-3.65 (t, J = 6.3 Hz, 2H, ImN-CH₂-(CH₂).,-^), 4.13-4.19 (t, J = 7.1 Hz, 2H, ImN-CH₂-CH₂-CH₂-NPhIt), 4.22-4.28 (t, J = 7.3 Hz, 2H, ImN-CH₂-CH₂- CH₂-NPlIt)₁ 7.78-7.81 (m, 2H, 2 * CH arom.), 7.83-7.92 (m, 4H, 4 x CH arom.), 9.15 (s, 1 H, 1 * CH arom.) ppm.

¹³C NMR (63 MHz, CD₃CN): δ 14.29, 23.13, 26.41 , 29.82, 30.49, 31.80, 35.32, 48.24, 50.73, 123.52, 123.58, 124.01 , 133.16, 135.39, 136.57, 169.52 ppm

ESI MS: In positive mode peaks at m/z 340.2 and 341.2 a.m.u. and in negative mode peak at m/z 144.7 a.m.u.

³¹P NMR (101 MHz, DMSO d₆): -159.97 to -117.87 ppm (septet)

¹⁹F NMR (235 MHz, DMSO c/₆): -67.92 to -64.90 ppm (doublet)

Characterization of 12d Melting point: 93-95 ⁰C

IR (KBr): 3164, 3109, 2924, 2857, 1770, 1718, 1615, 1568, 1469, 1441 , 1412, 1387, 1345, 1289, 1238, 1220, 1192, 1171 , 1143, 1111 , 1090, 1074, 1044, 971 , 837 cm^"1 ¹H NMR (250 MHz, DMSO d_β): δ 0.82-0.87 (t, J = 6.5 Hz, 3H, lmN-(CH₂)₇- CH₃), 1.25 (bs, 1OH, ImN-(CHz)₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₃), 1.76-1.84 (m, 2H, ImN-CH₂-CH₂-(CH₂)_S-CH₃), 2.13-2.24 (m, 2H, ImN-CH₂-CH₂-CH₂-NPW), 3.60-3.65 (t, J = 6.4 Hz, 2H₁ ImN-CH₂-(CH₂)_S-CH₃), 4.13-4.18 (t, J = 7.1 Hz, 2H, ImN-CH₂-CH₂-CH₂-NPlIt), 4.21-4.27 (t, J = 7.3 Hz, 2H, ImN-CH₂-CH₂- CH₂-NPlIt), 7.79-7.80 (m, 2H, 2 x CH arom.), 7.83-7.91 (m, 4H, 4 * CH arom.), 9.16 (s, 1H, 1 * CH arom.) ppm.

¹³C NMR (63 MHz, DMSO d_β): δ 13.94, 22.11 , 25.51 , 28.37, 28.52, 28.58, 29.33, 31.19, 34.31 , 46.64, 48.91 , 122.43, 122.45, 123.06, 131.75, 134.44, 136.19, 168.06 ppm

ESI MS: In positive mode peaks at m/z 368.2 and 369.2 a.m.u. and in negative mode peak at m/z 144.7 a.m.u.

³¹P NMR (101 MHz, DMSO cf₆): -159.97 to -117.87 ppm (septet)

¹⁹F NMR (235 MHz, DMSO d_β): -67.91 to -64.89 ppm (doublet)

Characterization of 12e Melting point: 105-107 ⁰C

IR (KBr): 3164, 3116, 2922, 2854, 1770, 1717, 1615, 1569, 1469, 1441 , 1412, 1387, 1345, 1289, 1239, 1192, 1172, 1144, 1111 , 1074, 1044, 971 , 838 cm^'1

¹H NMR (250 MHz, DMSO d_β): δ 0.82-0.87 (t, J = 6.4 Hz, 3H, ImN-(CHz)₉- CH₃), 1.23 (bs, 14H, ImN-(CHz)₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₃), 1.78-1.83 (m, 2H, ImN-CH₂-CH₂-(CH₂)_T-CH₃), 2.15-2.26 (m, 2H, ImN-CH₂- CH₂-CH₂-NPW), 3.61-3.66 (t, J = 6.4 Hz, 2H, ImN-CH₂-(CH₂)_S-CH₃), 4.14- 4.20 (t, J = 7.1 Hz, 2H, ImN-CH₂-CH₂-CH₂-NPW), 4.23-4.29 (t, J = 7.3 Hz, 2H, ImN-CH₂-CH₂-CH₂-NPlIt), 7.79-7.81 (m, 2H, 2 x CH arom.), 7.84-7.91 (m, 4H, 4 x CH arom.), 9.16 (s, 1 H, 1 x CH arom.) ppm.

¹³C NMR (63 MHz, DMSO d₆): δ 13.86, 22.06, 25.45, 28.35, 28.52, 28.66, 28.79, 28.86, 29.27, 31.26, 34.26, 46.62, 48.91 , 122.38, 122.41 , 123.00, 131.70, 134.37, 136.15, 167.97 ppm

ESI MS: In positive mode peaks at m/z 396.3 and 397.1 a.m.u. and in negative mode peak at m/z 144.7 a.m.u.

³¹P NMR (101 MHz, DMSOd₆): -160.23 to -118.14 ppm (septet)

19ι F NMR (235 MHz, DMSOd₆): -68.24 to -65.22 ppm (doublet)

Characterization of 13a

IR (Neat): 3645, 3590, 3398, 3336, 3161 , 3116, 2967, 2935, 2875, 1603, 1566, 1452, 1361 , 1333, 1252, 1171 , 1088, 1035, 833, 747, 649, 559 crτϊ¹

¹H NMR (250 MHz, DMSO d₆): δ 0.88-0.94 (t, J = 7.4 Hz, 3H, lmN-(CH₂)₃- CH₃), 1.21-1.35 (m, 2H, ImN-(CH₂J₂-CH₂-CH₃), 1.73-1.93 (m, 4H (2H are D₂O exchangeable) ImN-CH₂-CH₂-CH₂-CH₃ and ImN-CH₂-CH₂-NH₂), 2.90- 2.95 (t, J = 5.5 Hz, 2H, ImN-CH₂-CH₂-NH₂), 4.08-4.19 (m, 4H, ImN-CH₂-CH₂- NH₂ and ImN-CH₂-(CHz)₂-CH₃), 7.71-7.73 (m, 2H, 2 x CH arom.), 9.10 (s, 1 H, 1 x CH arom.) ppm.

¹³C NMR (63 MHz, DMSO d₆): δ 13.22, 18.80, 31.32, 41.16, 48.56, 52.01 , 122.09, 122.65, 136.18 ppm.

ESI MS: In positive mode peaks at m/z 169.1 , 168.1 and in negative mode peak at m/z 144.7 a.m.u.

³¹P NMR (101 MHz, DMSO d₆): -159.95 to -117.87 ppm (septet). ¹⁹F NMR (235 MHz, DMSO d₆): -67.98 to -64.97 ppm (doublet).

Characterization of 13b

IR (Neat): 3642, 3164, 2965, 2875, 1643, 1568, 1465, 1372, 1166, 1109, 842 cm^'1

¹H NMR (250 MHz, DMSO d₆): δ 0.88-0.94 (t, J = 7.3 Hz, 3H, lmN-(CH₂)₃- CH₃), 1.20-1.34 (m, 2H, ImN-(CHz)₂-CH₂-CH₃), 1.73-1.93 (m, 4H, ImN-CH₂- CH₂-CH₂-CH₃ and ImN-CH₂-CH₂-CH₂-NH₂), 2.28 (bs, 2H, D₂O exchangeable, ImN-CH₂-CH₂-CH₂-NH₂), 2.52-2.57 (t, J = 6.5 Hz, 2H, ImN-CH₂-CH₂-CH₂- NH₂), 4.14-4.20 (t, J = 7.3 Hz, 2H, lmN-CH₂-(CH₂)₂-CH₃) and 4.22-4.27 (t, J = 6.9 Hz, 2H, ImN-CH₂-CH₂-CH₂-NH₂), 7.76-7.77 (m, 2H, 2 x CH arom.), 9.17 (s, 1 H, 1 x CH arom.) ppm.

¹³C NMR (63 MHz, DMSO d₆): δ 13.22, 18.80, 31.28, 32.54, 37.80, 46.73, 48.65, 122.41 , 122.52, 136.05 ppm

ESI MS: In positive mode peaks at m/z 182.1 other peaks at 181.1 and 183.1 a.m. u. and in negative mode peak at m/z 144.7 a.m.u.

³¹P NMR (101 MHz, DMSO d₆): -159.97 to -117.87 ppm (septet)

¹⁹F NMR (235 MHz, DMSO d₆): -67.95 to -64.93 ppm (doublet)

Characterization of 13c

IR (Neat): 3390, 3164, 3118, 2959, 2933, 2862, 1645, 1567, 1468, 1380, 1247, 1165, 1111 , 1053, 841 , 776, 740 cm^"1

¹H NMR (250 MHz, DMSO d₆): δ 0.84-0.89 (t, J = 6.8 Hz, 3H, lmN-(CH₂)₅- CH₃), 1.27 (bs, 6H, ImN-CH₂-CH₂-CH₂-CH₂-CH₂-CH₃), 1.75-1.93 (m, 4H, ImN-CHz-CHHCH^-CHs and ImN-CH₂-CH₂-CH₂-NH₂), 2.36 (bs, 2H, D₂O exchangeable, ImN-CH₂-CH₂-CH₂-NH₂), 2.53-2.58 (t, J = 6.6 Hz, 2H, ImN- CH₂-CH₂-CH₂-NH₂), 4.13-4.19 (t, J = 7.1 Hz, 2H, ImN-CH₂-(CHz)₄-CH₃) 4.22- 4.27 (t, J = 6.9 Hz, 2H, ImN-CH₂-CH₂-CH₂-NH₂), 7.76-7.77 (m, 2H, 2 * CH arom.), 9.17 (s, 1H, 1 x CH arom.) ppm.

¹³C NMR (63 MHz, DMSO cf_β): δ 13.76, 21.87, 25.15, 29.24, 30.52, 32.45, 37.75, 46.70, 48.91 , 122.41 , 122.50, 136.04 ppm

ESI MS: In positive mode peaks at m/z 210.1 and 211.1 a.m.u. and in negative mode peak at m/z 144.7 a.m.u.

³¹P NMR (101 MHz, DMSO d₆): -159.97 to -117.87 ppm (septet)

¹⁹F NMR (235 MHz, DMSO d₆): -67.96 to -64.94 ppm (doublet)

Characterization of 13d

IR (Neat): 3390, 3164, 3118, 2929, 2858, 1646, 1567, 1468, 1366, 1247, 1165, 1111 , 1063, 1022, 840, 774, 740 cm ¹

¹H NMR (250 MHz, DMSO d₆): δ 0.83-0.88 (t, J = 6.5 Hz, 3H₁ lmN-(CH₂)₇- CH₃), 1.25 (bs, 10H, ImN-(CH₂J₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₃), 1.74-1.90 (m, 6H, ImN-CH₂-CH₂-(CHz)₅-CH₃, ImN-CH₂-CH₂-CH₂-NH₂ and ImN-CH₂-CH₂- CH₂-NH₂, two protons D₂O exchangeable), 2.50-2.55 (t, J = 6.4 Hz, 2H, ImN- CH₂-CH₂-CH₂-NH₂), 4.12^.18 (t, J = 7.1 Hz, 2H, ImN-CH₂-(CH₂)_G-CH₃), 4.20-4.26 (t, J = 7.0 Hz, 2H, ImN-CH₂-CH₂-CH₂-NH₂), 7.77-7.78 (m, 2H, 2 * CH arom.), 9.16 (s, 1 H, 1 * CH arom.) ppm.

¹³C NMR (63 MHz, DMSO d_β): δ 13.96, 22.12, 25.54, 28.36, 28.53, 29.34, 31.21 , 32.76, 37.85, 46.72, 48.91 , 122.43, 122.55, 136.08 ppm

ESI MS: In positive mode peaks at m/z 238.2 and 239.2 a.m.u. and in negative mode peak at m/z 144.7 a.m.u.

³¹P NMR (101 MHz, DMSOd₆): -159.99 to -117.88 ppm (septet) ¹⁹F NMR (235 MHz, DMSOd₆): -67.92 to -64.90 ppm (doublet)

Characterization of 13e IR (Neat): 3165, 2928, 2859, 1568, 1462, 1367, 1166, 1106, 841 cm -1

¹H NMR (250 MHz, CD₃CN): δ 0.85-0.90 (t, J = 6.1 Hz, 3H, lmN-(CH₂)₉-CH₃), 1.27 (bs, 14H, ImN-(CHz)₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₃), 1.77-1.96 (m, 4H, ImN-CH₂-CH₂-(CHz)₇-CH₃ and ImN-CH₂-CH₂-CH₂-NH₂), 2.43 (bs, 2H, ImN-CH₂-CH₂-CH₂-NH₂), 2.72 (bs, 2H, D₂O exchangeable, ImN-CH₂-CH₂- CH₂-NH₂), 4.09-4.15 (t, J = 7.4 Hz, 2H, ImN-CH₂-(CH₂)_S-CH₃), 4.22-4.27 (t, J = 7.0 Hz, 2H, ImN-CH₂-CH₂-CH₂-NH₂), 7.40-7.43 (m, 2H, 2 x CH arom.), 8.53 (s, 1 H, 1 x CH arom.) ppm.

¹³C NMR (63 MHz, CD₃CN): δ 14.23, 22.41 , 25.81 , 28.66, 28.98, 29.13, 29.20, 29.60, 31.61 , 32.79, 38.04, 46.99, 49.19, 122.73, 122.82, 136.36 ppm

ESI MS: In positive mode peaks at m/z 266.2 other peak at 267.1 a.m.u. and in negative mode peak at m/z 144.9 a.m.u.

³¹P NMR (101 MHz, DMSO d₆): -160.21 to -118.12 ppm (septet)

¹⁹F NMR (235 MHz, DMSO d₆): -68.19 to -65.18 ppm (doublet)

Characterization of 14a Melting point: 68-70 ⁰C

IR (KBr): 3159, 2981 , 2936, 2874, 1746, 1720, 1557, 1467, 1371 , 1333, 1288, 1229, 1154, 1072, 1035, 1002, 979, 839, 748, 656 crτϊ¹

¹H NMR (250 MHz, CDCI₃): δ 0.94-0.99 (t, J = 7.3 Hz, 3H, ImN-(CH₂J₃-CH₃), 1.26-1.44 (m, 2OH, ImN-(CHz)₂-CH₂-CH₃ and -N(CH₂COOC(CH₃)₃)₂), 1.84- 1.96 (m, 2H, ImN-CH₂-CH₂-CH₂-CH₃), 3.09-3.13 (m, 2H, ImN-CH₂-CH₂- N(CH₂COOC(CH₃)₃)2), 3.35 (s, 4H, lmN-CH₂-CH₂-N(CH₂COOC(CH₃)₃)₂), 4.13-4.22 (m, 4H, ImN-CH₂-CH₂-N(CH₂COOC(CH₃)_S)₂ and Im N-CH₂-(C H₂)₂- CH₃), 7.23-7.24 (m, 1H, 1 * CH arom.), 7.58-7.59 (m, 1 H₁ 1 x CH arom.), 9.09 (s, 1 H, 1 x CH arom.) ppm.

¹³C NMR (63 MHz, CDCI₃): δ 13.33, 19.40, 28.07, 31.70, 48.05, 49.76, 54.37, 56.52, 81.72, 121.15, 123.36, 136.59, 170.49 ppm

ESI MS: In positive mode peak at m/z 397.2, 396.2 other peaks at 340.2 and 284.1 a.m. u. and in negative mode peak at m/z 144.7 a.m.u.

³¹P NMR (101 MHz, CDCI₃): -164.90 to -122.76 ppm (septet).

¹⁹F NMR (235 MHz, CDCI₃): -74.85 to -71.83 ppm (doublet).

Characterization of 14b

IR (Neat): 3161 , 3117, 2977, 2937, 2877, 1731 , 1596, 1566, 1459, 1394, 1369, 1293, 1225, 1160, 1082, 1031 , 983, 939, 916, 840, 753, 740 cm ¹

¹H NMR (250 MHz, CDCI₃): δ 0.92-0.98 (t, J = 7.3 Hz, 3H, lmN-(CH₂)₃-CH₃), 1.26-1.48 (m, 2OH, -N(CH₂COOC(CH₃)₃)₂ and ImN-(CH₂J₂-CH₂-CH₃), 1.81- 2.04 (m, 4H, ImN-CH₂-CH₂-CH₂-CH₃ and ImN-CH₂-CH₂-CH₂- N(CH₂COOC(CH₃)₃)₂), 2.69-2.73 (t, J = 5.5 Hz, 2H, ImN-CH₂-CH₂-CH₂- N(CH₂COOC(CH₃)₃)₂), 3.29 (s, 4H, ImN-CH₂-CH₂-CH₂-

N(CH₂COOC(CH₃)₃)₂), 4.14^.20 (t, J = 7.3 Hz, 2H, ImN-CH₂-CH₂-CH₂-CH₃), 4.36-4.41 (t, J = 6.3 Hz, 2H, ImN-CH₂-CH₂-CH₂-N(CH₂COOC(CH₃)S)₂), 7.33 (s, 1 H, 1 x CH arom.), 7.48 (s, 1 H, 1 x CH arom.), 8.88 (s, 1 H, 1 x CH arom.) ppm.

¹³C NMR (63 MHz, CDCI₃): δ 13.30, 19.40, 27.57, 28.11, 31.74, 47.66, 49.78, 50.48, 55.95, 81.47, 122.10, 122.78, 136.17, 170.56 ppm ESI MS: In positive mode peaks at m/z 410.2 and 411.2 a.m.u. and in negative mode peak at m/z 144.7 a.m.u.

³¹P NMR (101 MHz, CDCI₃): -164.99 to -122.85 ppm (septet)

¹⁹F NMR (235 MHz, CDCI₃): -74.98 to -71.96 ppm (doublet)

Characterization of 14c

IR (Neat): 3156, 3117, 2976, 2934, 2872, 1731 , 1595, 1566, 1458, 1394, 1369, 1225, 1160, 1082, 1034, 983, 938, 916, 839, 753, 740 cm^"1

¹H NMR (250 MHz, CDCI₃): δ 0.84-0.90 (t, J = 6.5 Hz, 3H, ImN-(CH₂)_S-CH₃), 1.32 (bs, 4H, ImN-(CH₂)_S-CH₂-CH₂-CH₃), 1.45-1.49 (m, 2OH, - N(CH₂COOC(CH₃)₃)₂ and lmN-(CH₂)₂-CH₂-(CH₂)₂-CH₃), 1.86-2.05 (m, 4H, ImN-CH₂-CH₂-(CHz)₃-CH₃ and ImN-CH₂-CH₂-CH₂-N(CH₂COOC(CH₃)_S)₂), 2.69-2.74 (t, J = 6.0 Hz, 2H, ImN-CH^CH^CHs-N^^COOC^Hs)^), 3.30 (s, 4H, ImN-CH₂-CH₂-CH₂-N(CH₂COOC(CH₃)_S)₂), 4.14^.20 (t, J = 7.4 Hz, 2H, ImN-CHHCH^-CHs), 4.36^.41 (t, J = 6.1 Hz, 2H, ImN-CH₂-CH₂-CH₂- N(CH₂COOC(CHs)s)₂), 7.37 (s, 1 H₁ 1 x CH arom.), 7.48 (s, 1H₁ 1 * CH arom.), 8.88 (s, 1 H, 1 * CH arom.) ppm.

¹³C NMR (63 MHz, acetone cf_β): δ 14.16, 22.96, 26.43, 28.16, 28.26, 30.46, 31.74, 48.30, 50.41 , 51.01 , 56.14, 81.29, 123.18, 123.46, 137.36, 171.12 ppm

ESI MS: In positive mode peaks at m/z 438.3 and 439.3 a.m.u. and in negative mode peak at m/z 144.7 a.m.u.

³¹P NMR (101 MHz, CDCI₃): -164.91 to -122.76 ppm (septet)

¹⁹F NMR (235 MHz, CDCI₃): -74.76 to -71.74 ppm (doublet) Characterization of 14d

IR (Neat): 3160, 3117, 2931 , 2859, 1733, 1566, 1458, 1394, 1369, 1225, 1159, 1083, 1033, 982, 938, 916, 841 , 753, 740 cm-¹

¹H NMR (250 MHz, CD₃CN): δ 0.84-0.89 (t, J = 6.1 Hz, 3H, ImN-(CH₂)_T-CH₃), 1.27-1.29 (m, 8H, ImN-(CHz)₃-CH₂-CH₂-CH₂-CH₂-CH₃), 1.42-1.46 (m, 2OH, - N(CH₂COOC(CH₃)₃)₂ and ImN-tCHzh-CHHCH^-CH^, 1.76-1.97 (m, 4H, ImN-CH₂-CH₂-(CH₂)S-CH₃ and ImN-CH₂-CH₂-CH₂-N(CH₂COOC(CH₃)S)₂), 2.62-2.67 (t, J = 6.1 Hz, 2H, lmN-CH₂-CH₂-CH₂-N(CH₂COOC(CH₃)₃)₂), 3.27 (s, 4H, lmN-CH₂-CH₂-CH₂-N(CH₂COOC(CH₃)₃)₂), 4.06-4.12 (t, J = 7.4 Hz, 2H, lmN-CH₂-(CH₂)₆-CH₃), 4.23-4.28 (t, J = 6.6 Hz, 2H, ImN-CH₂-CH₂-CH₂- N(CH₂COOC(CH₃)s)₂), 7.34-7.35 (m, 1 H₁ 1 x CH arom.), 7.40-7.41 (s, 1H, 1 x CH arom.), 8.65 (s, 1 H, 1 * CH arom.) ppm.

¹³C NMR (63 MHz, CD₃CN): δ 14.41 , 23.34, 26.79, 28.21 , 28.41 , 29.60, 29.77, 30.50, 32.46, 48.42, 50.61 , 51.24, 56.50, 81.80, 123.22, 123.52, 137.14, 171.57 ppm

ESI MS: In positive mode peaks at m/z 466.3 and 467.3 a.m.u. and in negative mode peak at m/z 144.7 a.m.u.

³¹P NMR (101 MHz, CDCI₃): -164.95 to -122.79 ppm (septet)

¹⁹F NMR (235 MHz, CDCI₃): -74.94 to -71.91 ppm (doublet)

Characterization of 14e

IR (Neat): 3155, 3116, 2926, 2856, 1735, 1565, 1458, 1394, 1368, 1224, 1159, 1082, 983, 938, 916, 839 cm ¹

¹H NMR (250 MHz, CD₃CN): δ 0.85-0.91 (t, J = 6.4 Hz, 3H, ImN-(CHz)₉-CH₃), 1.28 (bs, 12H, ImN-(CH₂)S-CH₂-CH₂-CH₂-CH₂-CHrCH₂-CH₃), 1.44 (bs, 2OH, - N(CH₂COOC(CH₃)₃)₂ and lmN-(CH₂)₂-CH₂-(CH₂)₆-CH₃), 1.82-2.00 (m, 4H, ImN-CH₂-CH₂-(CH₂)T-CH₃ and lmN-CH₂-CH₂-CH₂-N(CH₂COOC(CH₃)₃)₂), 2.65-2.70 (t, J = 6.3 Hz, 2H, ImN-CH₂-CH₂-CH₂-N(CH₂COOC(CH₃)_S)₂), 3.30 (s, 4H, lmN-CH₂-CH₂-CH₂-N(CH₂COOC(CH₃)₃)₂), 4.09-4.15 (t, J = 7.4 Hz, 2H, ImN-CH₂-(CH₂)B-CH₃), 4.25^.31 (t, J = 6.5 Hz, 2H, ImN-CH₂-CH₂-CH₂- N(CH₂COOC(CH₃)3)2), 7.37-7.38 (m, 1 H, 1 x CH arom.), 7.43-7.44 (m, 1 H, 1 x CH arom.), 8.69 (s, 1H, 1 * CH arom.) ppm.

¹³C NMR (63 MHz, CD₃CN): δ 14.50, 23.42, 26.80, 28.17, 28.44, 29.65, 30.03, 30.12, 30.23, 30.51, 32.65, 48.40, 50.60, 51.27, 56.47, 81.83, 123.22, 123.51 , 137.14, 171.48 ppm

ESI MS: In positive mode peaks at m/z 494.5 and 495.3 a.m.u. and in negative mode peak at m/z 144.7 a.m.u.

³¹P NMR (101 MHz, CDCI₃): -164.86 to -122.72 ppm (septet)

¹⁹F NMR (235 MHz, CDCI₃): -74.61 to -71.59 ppm (doublet)

Characterization of 15ai

ESI MS: In positive mode peaks at m/z 628.0 (M+1 , ⁶³Cu), 629.1 (M+2, ⁶³Cu), 630.1 (M+1 , ⁶⁵Cu), 631.1 (M+2, ⁶⁵Cu) other peaks at 283.1 , 284.1 and 285.1 a.m.u.

Characterization of 15a₂

ESI MS: In positive mode peaks at m/z 623.0 (M+1 , ⁵⁸Ni), 624.1 (M+2, ⁵⁸Ni), 625.0 (M+1 , ⁶⁰Ni), 626.0 (M+2, ⁶⁰Ni) other peaks at 283.2, 284.1 and 285.1 a.m.u.

Characterization of 15a₃

ESI MS: In positive mode peaks at m/z 623.1 (M, ⁵⁹Co), 624.0 (M+1 , ⁵⁹Co), 625.0 (M+2, ⁶⁹Co) other peaks at 283.1 , 284.1 and 285.1 a.m.u. Characterization of 15b

ESI MS: In positive mode peaks at 656.2 (M+1 , ⁶³Cu), 657.2 (M+2, ⁶³Cu), 658.2 (M+1 , ⁶⁵Cu), 659.2 (M+2, ⁶⁵Cu).

Characterization of 15c

ESI MS: In positive mode peaks at 712.3 (M+1 , ⁶³Cu), 713.3 (M+2, ⁶³Cu), 714.3 (M+1 , ⁶⁵Cu), 715.3 (M+2, ⁶⁵Cu).

Characterization of 15d

ESI MS: In positive mode peaks at 768.3 (M+1 , ⁶³Cu), 769.3 (M+2, ⁶³Cu), 770.3 (M+1 , ⁶⁵Cu), 771.3 (M+2, ⁶⁵Cu) a.m.u..

Characterization of 15e

For the Cu complex: In positive mode peaks at 824.4 (M+1 , ⁶³Cu), 825.4 (M+2, ⁶³Cu), 826.4 (M+1 , ⁶⁵Cu), 827.4 (M+2, ⁶⁵Cu) a.m.u.

As it can be seen from Figs. 1 and 2 and Schemes 1 and 2, increase in alkyl chain length can cause:

improvement in the liquids properties of ionic liquids increase in the hydrophobicity of the complexes which may cause:

- improved partitioning of the complexes in the organic phase; and

- insolubility of the complexes in aqueous phase.

Concerning the octahedral complex (see Fig. 1), which sits around a crystallographic center of inversion, features a 2:1 ratio of the chelating TSIL- based (Task Specific Ionic Liquid) ligand to Cu with two unidentate carboxylate ligands in axial positions and two other unidentate carboxylate ligands occupying equatorial positions in a trans configuration. The remaining coordination sites in the octahedral complex are occupied by two equatorial amine ligands. Since the ligand used to chelate the metal is a novel zwitterionic imidazolium ethylamine dicarboxylate ligand with a -1 overall charge, the resulting complex is overall neutral. Thus, a counter ion is neither required nor observed for this chelate complex. It is likely that the hexafluorophosphate ion was removed NH4PF6 (aq) during the formation of the complex. The octahedral complex and included water molecules assemble via 0-H- O hydrogen bonds to form a two-dimensional structure.

A particularly interesting feature of the X-ray structure is that the alkyl substituents on the imidazolium rings are oriented away from, rather than towards or wrapped around, the center of the complex. The position of the alkyl groups has enabled us to rationally "re-design" the TSIL ligand to contain a longer alkyl chain, n-butyl. Lengthening the alkyl chain renders the complexes formed with Co, Ni, or Cu more hydrophobic and also soluble in 1-butanol. Whereas the complexes derived from 1 are water soluble and 1-butanol insoluble, it was determined that those prepared from a derivative containing a butyl chain in the 1 -position of the imidazolium ring are soluble in 1-butanol. The formation of these 2:1 complexes using the C4-derivatives has been confirmed using ESI-MS. Yet other analogues have allowed metal ions to be removed directly from aqueous phases with separation into a phase containing the 2:1 complexes (i.e. with C-10 alkyl chains). These TSILs where then used to extract Co, Ni, or Cu from aqueous solutions.

As it can be seen from Fig. 2, it is clear that the complexes derived from the compounds 14b, 14c, 14d and 14e behave differently as far as their solubility behavior is concerned. It can be seen that complexes 15b, 15c, and 15d are water soluble, while complex 15e is highly hydrophobic and thus water insoluble. Complex 15e easily precipitates out of water upon formation.

It was thus shown that imidazolium based TSILs containing an ethylaminediacetic acid moiety form metal chelate complexes. With appropriate inclusion of hydrophobic alkyl groups the properties of these TSILs have been altered to enable these complexes to separate from an aqueous layer upon formation. It was thus possible to perform such a rational "re-design" of these TSILs based on analysis of the crystal structure obtained for the prototype chelate complex, 6a. A "re-design" of this nature, or otherwise, has not previously been possible for other TSILs that either coordinate or chelate metals due to the lack of crystallographic data (i.e. no crystal structures for these other complexes have yet been reported to our knowledge). It was also shown that it is possible to prepare TSILs with desirable solubility and recyclability properties capable of remediating water contaminated with various metal ions. The presence of the ethylaminediacetic acid moiety also permits the metals to be selectively and reversibly complexed through careful control of pH. It is also possible to extend this methodology to TSILs derived from tetraalkylammonium, pyridinium, pyrollidinium, and phosphonium salts.

While the invention has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modifications and this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains and as may be applied to the essential features hereinbefore set forth, and as follows in the scope of the appended claims.

Claims

WHAT IS CLAIMED IS:

1. A compound of formula (I):

wherein

R¹ is a positively charged heterocyclic ring, which is unsubstituted or substituted with 1 to 3 substitutents selected from the group consisting of halogen atom, -NO2, -CN -OH₁ -CF₃ -COR⁴, -SH, -OMe, -SMe, -SPh, -COOH, -COOR⁴, -NH₂, -NHR⁵, -N(R⁵)₂, C₂- C₂₀ alkenyl, Ci-C₂₀ alkoxy, C₁-C₂O alkyl, C₂-C₂O alkynyl, C₆-C₂₀ aralkyl, C₆-Ci₂ aryl, C₃-Cs cycloalkyl, Ci-C₂₀ aminoalkyl, Ci-C₆ hydroxyalkyl, C₁-C₁₂ heteroaryl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S, and CrCi₂ heterocyclyl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S

R² and R³ are the same or different and are selected from the group consisting of a -OH, -SH, -OR⁶, -SR⁶, -NH₂, -NHR⁵, -N(R⁵)₂₎ -0(C=O)R⁴.

R⁴ is a Ci-C₂₀ alkyl which is linear or branched, C₃-Ci₂ cycloalkyl, CrCi₂ heterocyclyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆-C₁₂ aryl, C₆-C₂₀ aralkyl, C₆-C₂₀ alkylaryl, and C₁-Ci₂ heteroaryl,

R⁵ is a CrC₂₀ alkyl which is linear or branched, C₃-Ci₂ cycloalkyl, C₁-Ci₂ heterocyclyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆-C₁₂ aryl, C₆-C₂₀ aralkyl, C₆-C₂₀ alkylaryl, C₁-Ci₂ heteroaryl, and a suitable protecting group for an amine; R⁶ is a C1-C2₀ alkyl which is linear or branched, C₃-Ci₂ cycloalkyl, C1-C12 heterocyclyl, C₂-C₂O alkenyl, C₂-C₂₀ alkynyl, C₆-Ci₂ aryl, C₆-C₂₀ aralkyl, C₆-C_2O alkylaryl, Ci-Ci₂ heteroaryl, and a suitable protecting group for a hydroxy group or a thiol group;

X¹ is an anion selected from the group consisting of F^", Cl^" , Br^', r, CIO₄-, PF₆-, N₃-, BF₄ ^", SbF₆ ^", BH₄ ^", (FSO₂)₂N-, (CF₃SO₂)₂N-, (C₂F₅SO₂)₂N-, (CF₃SO₂)₃C-, CF₃SO₃-, CF₃COO-, AsF₆ ^", CH₃COO-, (CN)₂N^", NO₃ ^";

X² and X³ are the same or different and each represent an oxygen atom or a sulphur atom

m is an integer having a value from 1 to 3;

n is an integer having a value from 1 to 3; and

p is an integer having a value from 1 to 12.

2. The compound of claim 1 , wherein R² and R³ are the same.

3. The compound of claim 1 or 2, wherein X² and X³ are the same.

4. The compound of any one of claims 1 to 3, wherein m and n have the same value.

5. The compound of any one of claims 1 to 4, wherein R¹ is a nitrogen- containing charged heterocyclic ring.

6. The compound of any one of claims 1 to 4, wherein R¹ is of formula :

wherein

each formula is as presented above or substituted with 1 to 3 substituents as defined for R¹ in claim 1 ;

R⁷ represents a hydrogen atom, halogen atom, -NO2, -CN -OH, -CF₃ -COR⁴, -SH, -OMe, -SMe, -SPh, -COOH, -COOR⁴, -NH₂, -NHR⁵, -N(R⁵)₂, C₂-C₂₀ alkenyl, Ci-C₂₀ alkoxy, Ci-C₂₀ alkyl, C₂-C₂₀ alkynyl, C₆-C₂₀ aralkyl, C₆-Ci₂ aryl, C₃-C₈ cycloalkyl, CrC₂₀ aminoalkyl, CrC₆ hydroxyalkyl, Ci-Ci₂ heteroaryl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S, and CrCi₂ heterocyclyl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S;

R⁸, R⁹, and R¹⁰ are same or different and each independently represent a CrC₂₀ alkyl which is linear or branched, C₃- C₁₂ cycloalkyl, CrCi₂ heterocyclyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, Cβ- C-₁₂ aryl, C₆-C₂0 aralkyl, Ce-C₂₀ alkylaryl, CrCi₂ heteroaryl, and a suitable protecting group for an amine;

R¹¹, R¹², and R¹³ are same or different and each independently represent a CrC₂₀ alkyl which is linear or branched, C₃- C₁₂ cycloalkyl, C₁-C₁₂ heterocyclyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆- Ci2 aryl, C₆-C₂O aralkyl, C₆-C₂O alkylaryl, C_rCi₂ heteroaryl, and a suitable protecting group for a phosphorus atom;

R¹⁴ and R¹⁵ are same or different and each independently represent a CrC_2O alkyl which is linear or branched, C₃-C₁₂ cycloalkyl, Ci-Ci₂ heterocyclyl, C₂-C₂O alkenyl, C₂-C₂O alkynyl, C₆-Ci₂ aryl, C₆-C_2O aralkyl, C₆-C_2O alkylaryl, CrCi₂ heteroaryl, and a suitable protecting group for a sulphur atom; and

R⁴, R⁵, R⁶ and X₂ is as previously defined in claim 1.

7. The compound of any one of claims 1 to 4, wherein R¹ is of formula :

wherein

R⁷ represents a hydrogen atom, halogen atom, -NO₂, -CN -OH, -CF₃ -COR⁴, -SH, -OMe, -SMe, -SPh, -COOH, -COOR⁴, -NH₂, -NHR⁵, -N(R⁵)₂, C₂-C₂₀ alkenyl, C₁-C₂₀ alkoxy, C₁-C₂₀ alkyl, C₂-C₂₀ alkynyl, C₆-C₂₀ aralkyl, C₆-C₁₂ aryl, C₃-Ce cycloalkyl, Ci-C₂₀ aminoalkyl, C₁-C₆ hydroxyalkyl, CrC₁₂ heteroaryl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S, and C₁-Ci₂ heterocyclyl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S; R⁸, R⁹, and R¹⁰ are same or different and each independently represent a C1-C20 alkyl which is linear or branched, C₃- C12 cycloalkyl, C1-C12 heterocyclyl, C₂-C₂O alkenyl, C₂-C₂O alkynyl, C₆- Ci₂ aryl, C₆-C₂₀ aralkyl, C6-C₂o alkylaryl, C₁-Ci₂ heteroaryl, and a suitable protecting group for an amine;

R¹¹, R¹², and R¹³ are same or different and each independently represent a C1-C₂0 alkyl which is linear or branched, C₃- C₁₂ cycloalkyl, Ci-Ci₂ heterocyclyl, C₂-C_2O alkenyl, C₂-C₂₀ alkynyl, C₆- Ci₂ aryl, C₆-C₂₀ aralkyl, C₆-C_2O alkylaryl, C_rCi₂ heteroaryl, and a suitable protecting group for a phosphorus atom;

R¹⁴ and R¹⁵ are same or different and each independently represent a CrC_2O alkyl which is linear or branched, C₃-Ci₂ cycloalkyl, Ci-Ci₂ heterocyclyl, C₂-C₂O alkenyl, C₂-C_2O alkynyl, C₆-Ci₂ aryl, C₆-C₂₀ aralkyl, C₆-C_2O alkylaryl, Ci-Ci₂ heteroaryl, and a suitable protecting group for a sulphur atom; and

R⁴, R⁵, R⁶ and X₂ is as previously defined in claim 1.

8. The compound of any one of claims 1 to 4, wherein R¹ is of formula :

wherein R¹⁶ is a C₁-C₄ alkyl group.

9. The compound of claim 8, wherein R¹⁶ is methyl.

10. The compound of claim 8, wherein R¹⁶ is butyl.

11. The compound of any one of claims 1 to 4, wherein R¹ is of formula :

wherein R¹⁶ is a C₁-C₁₂ alkyl group.

12. The compound of claim 11 , wherein R¹⁶ is hexyl, octyl, or decyl.

13. The compound of any one of claims 1 to 12, wherein R² and R³ are the same and they each represent -OH or -OR⁶, wherein R⁶ is a d- C₈ linear or branched alkyl group.

14. The compound of any one of claims 1 to 12, wherein X² and X³ are the same and they each represent an oxygen atom.

15. The compound of any one of claims 1 to 14, wherein X¹ is selected from the group consisting of F^", Cl^", Br^", I^", (CN)₂N^", BF₄ ^", (CF₃SO₂HN^" and PF₆ ^".

16. The compound of any one of claims 1 to 15, wherein X¹ is PF₆ ^".

17. The compound of any one of claims 1 to 16, wherein m and n have a value of 1.

18. The compound of any one of claims 1 to 17, wherein p has a value of 1 to 3.

19. The compound of any one of claims 1 to 17, wherein p has a value of 2.

20. The compound of any one of claims 1 to 17, wherein p has a value of 3.

21. A process for preparing a compound of formula (I)₁ as defined in any one of claims 1 to 20, comprising the step of reacting together compounds of formulas (II), (III), and (IV):

(II) (III) (IV)

wherein

L¹ and L² are the same or different and each represent a leaving group.

R¹, R², R³, X¹, X², X³, m, n and p are as previously defined.

22. The process of claim 21 , wherein compounds of formulas (III) and (IV) are identical.

23. The process of claim 21 or 22, wherein L¹ is selected from the group consisting of Cl, Br, I, tosylate, mesylate, brosylate, and OH₂.

24. The process of claim 23, wherein L¹ is Cl or Br.

25. The process of claim 21 or 22 wherein L² is selected from the group consisting of Cl, Br, I, tosylate, mesylate, brosylate, and OH₂.

26. The process of claim 25, wherein L² is Cl or Br.

27. A process for preparing a compound of formula (I), as defined in any one of claims 1 to 20, comprising the step of reacting together compounds of formulas (V) and (Vl):

(V) (VI)

wherein

L³ represents a leaving group; and

R )1¹, 2 3

X V^ , X V^ύ, m, n and p are as previously defined.

28. The process of claim 27, wherein L³ is selected from the group consisting of Cl, Br, I, tosylate, mesylate, brosylate, and OH₂.

29. The process of claim 27, wherein L³ is Cl or Br.

30. Use of a compound of any one of claims 1 to 20, for complexing a cation.

31. The use of claim 30, wherein said cation is a cation of a metal selected from the group consisting of Li, Na, K, Rb, Cs, Fr₁ Be, Mg, Ca, Sr, Ba, Ra, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La₁ Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Ac₁ Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr, Al, Ga, In, Ti, Sn₁ and Pb.

32. The use of claim 31 , wherein said cation is a bivalent cation.

33. The use of claim 31 , wherein said cation is selected from the group consisting of Cu²⁺, Ni²⁺, and Co²⁺.

34. Use of a compound of any one of claims 1 to 20, for purifying air.

35. Use of a compound of any one of claims 1 to 20, for decontaminating a liquid by extracting a metal present in said liquid with said compound.

36. Use of a compound of any one of claims 1 to 20 as an ionic liquid.

37. A method for at least partially extracting a metal from a composition comprising said metal and a liquid, said method comprising reacting said composition with a compound as defined in any one of claims 1 to 20 so as to form a complex and separating the obtained complex from the rest of said composition.

38. A method for decontaminating a liquid that is contaminated with a metal, said method comprising the step of extracting said metal by means of a compound as defined in any one of claims 1 to 20.

39. The method of claim 38, wherein said step of extracting comprises reacting said compound as defined in any one of claims 1 to 20, together with said metal so as to form a complex and then, separating said complex from said liquid.

40. The method of any one of claims 37 to 39, wherein said cation is a cation of a metal selected from the group consisting of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr, Al, Ga, In, Ti, Sn, and Pb.

41. The method of any one of claims 37 to 39, wherein said metal is a bivalent cation.

42. The method of any one of claims 37 to 39, wherein said metal is selected from the group consisting of Cu²⁺, Ni²⁺, and Co²⁺.

43. A kit for extracting a metal comprising a compound as defined in any one of claims 1 to 20, together with instructions indicating how to use such a compound.

44. A kit for decontaminating a liquid contaminated with a metal, said kit comprising a compound as defined in any one of claims 1 to 20, together with instructions indicating how to use such a compound.

45. A complex comprising a metal complexed by two compounds as those defined in any one of claims 1 to 20.

46. The complex of claim 45, wherein the two compounds complexing said metal are identical.

47. The complex of claim 45 or 46, wherein said metal is selected from the group consisting of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm₁ Md, No, Lr, Al, Ga, In, Ti, Sn, and Pb.

48. The complex of any one of claims 45 to 47, wherein said metal is a bivalent cation.

49. The complex of claim 45 or 46, wherein said metal is selected from the group consisting of Cu²⁺, Ni²⁺, and Co²⁺.

50. A complex of formula (VII):

(VII)

wherein R¹⁷ is a positively charged heterocyclic ring, which is unsubstituted or substituted with 1 to 3 substitutents selected from the group consisting of halogen atom, -NO₂, -CN -OH, -CF₃ -COR⁴, -SH, - OMe, -SMe, -SPh, -COOH, -COOR⁴, -NH₂, -NHR⁵, -N(R⁵)₂, C₂-

C_2O alkenyl, Ci-C₂₀ alkoxy, C1-C20 alkyl, C₂-C₂₀ alkynyl, C₆-C₂₀ aralkyl, C₆-C₁₂ aryl, C₃-C₈ cycloalkyl, CrC₂₀ aminoalkyl, Ci-C₆ hydroxyalkyl, Ci-Ci₂ heteroaryl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S, and C_rCi₂ heterocyclyl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S

R⁴ is a CrC₂₀ alkyl which is linear or branched, C₃-Ci₂ cycloalkyl, CrCi₂ heterocyclyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆-Ci₂ aryl, C₆-C₂₀ aralkyl, C₆-C₂₀ alkylaryl, and CrCi₂ heteroaryl,

R⁵ is a CrC₂₀ alkyl which is linear or branched, C₃-Ci₂ cycloalkyl, CrCi₂ heterocyclyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆-Ci₂ aryl, C₆-C₂₀ aralkyl, C₆-C₂₀ alkylaryl, CrCi₂ heteroaryl, and a suitable protecting group for an amine;

X⁴ is an oxygen atom or a sulphur atom;

X⁵ is the same or different and are selected from the group consisting of a -OH, -SH, -OR⁶, -SR⁶, -NH₂, -NHR⁵, -N(R⁵)_2f -0(C=O)R⁴.

q is an integer having a value from 1 to 12; and r is an integer having a value from 1 to 3.

51. The complex claim 50, wherein R 17 is of formula

wherein

each formula is as presented above or substituted with 1 to 3 substituents as defined for R¹⁷ in claim 46;

R⁷ represents a hydrogen atom, halogen atom, -NO₂, -CN -OH, -CF₃ -COR⁴, -SH, -OMe, -SMe, -SPh, -COOH, -COOR⁴, -NH₂, -NHR⁵, -N(R⁵)₂, C₂-C₂₀ alkenyl, Ci-C₂₀ alkoxy, C₁-C₂₀ alkyl, C₂-C₂₀ alkynyl, C₆-C₂₀ aralkyl, C₆-C₁₂ aryl, C3-C₈ cycloalkyl, CrC₂₀ aminoalkyl, CrC₆ hydroxyalkyl, C₁-Ci₂ heteroaryl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S₁ and CrC₁₂ heterocyclyl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S;

R⁸, R⁹, and R¹⁰ are same or different and each independently represent a C₁-C₂₀ alkyl which is linear or branched, C₃- C₁₂ cycloalkyl, C₁-C₁₂ heterocyclyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆- C₁₂ aryl, C₆-C₂₀ aralkyl, C₆-C₂₀ alkylaryl, CrC₁₂ heteroaryl, and a suitable protecting group for an amine; R¹¹, R¹², and R¹³ are same or different and each independently represent a C₁-C2₀ alkyl which is linear or branched, C₃- C₁₂ cycloalkyl, C1-C12 heterocyclyl, C2-C20 alkenyl, C₂-C₂O alkynyl, C₆- C₁₂ aryl, C₆-C₂O aralkyl, C₆-C2o alkylaryl, C1-C12 heteroaryl, and a suitable protecting group for a phosphorus atom;

R¹⁴ and R¹⁵ are same or different and each independently represent a C₁-C₂₀ alkyl which is linear or branched, C₃-C₁2 cycloalkyl, Ci-Ci2 heterocyclyl, C₂-C₂O alkenyl, C₂-C₂O alkynyl, C₆-Ci₂ aryl, C₆-C₂₀ aralkyl, C₆-C₂₀ alkylaryl, C₁-Ci₂ heteroaryl, and a suitable protecting group for a sulphur atom; and

R⁴, R⁵ and X₂ is as previously defined in claim 46.

52. The complex of claim 50, wherein R 17 is of formula

wherein

R⁷ represents a hydrogen atom, halogen atom, -NO₂, -CN -OH, -CF₃ -COR⁴, -SH, -OMe, -SMe, -SPh, -COOH, -COOR⁴, -NH₂, -NHR⁵, -N(R⁵)₂, C₂-C₂₀ alkenyl, C₁-C₂₀ alkoxy, C₁-C₂₀ alkyl, C₂-C₂₀ alkynyl, C6-C20 aralkyl, C6-C12 aryl, C₃-C₈ cycloalkyl, C1-C20 aminoalkyl, CrC₆ hydroxyalkyl, C1-C12 heteroaryl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S, and C₁-C₁₂ heterocyclyl comprising 1 to 4 heteroatoms selected from the group consisting of N, O and S;

R⁸, R⁹, and R¹⁰ are same or different and each independently represent a C1-C20 alkyl which is linear or branched, C₃- C12 cycloalkyl, C1-C12 heterocyclyl, C2-C20 alkenyl, C2-C20 alkynyl, C₆- C₁₂ aryl, C₆-C_2O aralkyl, C6-C20 alkylaryl, C1-C12 heteroaryl, and a suitable protecting group for an amine;

R¹¹, R¹², and R¹³ are same or different and each independently represent a Ci-C₂o alkyl which is linear or branched, C₃- Ci₂ cycloalkyl, C1-C12 heterocyclyl, C2-C2₀ alkenyl, C₂-C_2O alkynyl, C₆- Ci₂ aryl, C₆-C_2O aralkyl, C₆-C₂O alkylaryl, Ci-Ci₂ heteroaryl, and a suitable protecting group for a phosphorus atom;

R¹⁴ and R¹⁵ are same or different and each independently represent a Ci-C₂o alkyl which is linear or branched, C₃-Ci₂ cycloalkyl, Ci-Ci₂ heterocyclyl, C₂-C₂O alkenyl, C₂-C₂₀ alkynyl, C₆-Ci₂ aryl, C₆-C₂₀ aralkyl, C₆-C_2O alkylaryl, Ci-Ci₂ heteroaryl, and a suitable protecting group for a sulphur atom; and

R⁴, R⁵ and X₂ is as previously defined in claim 46.

53. The complex of any one of claims 50 to 52, wherein R¹⁷ is of formula :

wherein R¹⁶ is a CrC₄ alkyl group.

54. The complex of claim 53, wherein R¹⁶ is methyl.

55. The complex of claim 53, wherein R¹⁶ is butyl.

56. The complex of any one of claims 50 to 52, wherein R¹⁷ is of formula :

wherein R¹⁶ is a C₁-C1₂ alkyl group.

57. The complex of claim 56, wherein R¹⁶ is hexyl, octyl or decyl.

58. The complex of claim 50, wherein R¹⁷ is a nitrogen-containing charged heterocyclic ring.

59. The complex of any one of claims 50 to 58, wherein X⁴ is an oxygen atom.

60. The complex of any one of claims 50 to 59, wherein X⁵ is an oxygen atom.

61. The complex of any one of claims 50 to 60, wherein r has a value of 1.

62. The complex of any one of claims 50 to 61 , wherein q has a value of 2.

63. The complex of any one of claims 50 to 61 , wherein q has a value of 3.

64. The complex of any one of claims 50 to 63, wherein said metal is selected from the group consisting of Cu²⁺, Ni²⁺, and Co²⁺.

65. Use of a complex of any one of claims 50 to 64, for purifying air.

66. Use of a complex of any one of claims 50 to 64, for catalysis in organic synthetic transformations or gas purifications.