WO2014167034A2

WO2014167034A2 - Fluoro and chloro cyano compounds of the 15th group

Info

Publication number: WO2014167034A2
Application number: PCT/EP2014/057219
Authority: WO
Inventors: Katharina SIEVERT; Axel Schulz; Jörg HARLOFF; Alrik STOFFERS; Stefan Ellinger; Lothar Ott; Christiaan RIJKSEN; Patrick Franke; Christoph Taeschler; Cornelia Zur Taeschler
Original assignee: Lonza Ltd
Priority date: 2013-04-12
Filing date: 2014-04-10
Publication date: 2014-10-16
Also published as: WO2014167035A1; WO2014167034A3

Abstract

The invention discloses certain fluoro and chloro cyano compounds of the 15th group of the periodic table with 1 to 5 cyano residues, represented by formula (I), by a reaction using trimethylsilylcyanide, a method for their preparation; the compounds are used as ionic liquids; [Catⁿ⁺] [(Z¹(Q¹)_6-m(CN)_m)^- ]_n (I) Catⁿ⁺ is a cation, Z¹ is P, As, Sb or Bi, Q¹ is fluoro or chloro, m is 1, 2, 3 or 5 and n is 1, 2, 3 or 4.

Description

FLUORO AND CHLORO CYANO COMPOUNDS OF THE 15TH GROUP

The invention discloses certain fluoro and chloro cyano compounds of the 15th group of the periodic table with 1 to 5 cyano residues, represented by formula (I), by a reaction using trimethylsilylcyanide, a method for their preparation;the compounds are used as ionic liquids;

n+ _{j j}

Cat is a cation, Z is P, As, Sb or Bi, Q is fluoro or chloro, m is 1, 2, 3, or 5 and n is 1, 2, 3 or 4. BACKGROUND OF THE INVENTION

The term "ionic liquid" (IL) is usually used to refer to a salt which is liquid at temperatures below 100°C, in particular at room temperature. Such liquid salts typically comprise organic cations and organic or inorganic anions, and are described inter alia in P. Wasserscheid et al., Angew. Chem., 2000, 112, 3926-3945.

Ionic liquids have a series of interesting properties: Usually, they are thermally stable, relatively non-flammable and have a low vapor pressure. They show good solvability for numerous organic and inorganic substances. In addition, ionic liquids have interesting electrochemical properties, for example electrical conductivity which is often accompanied by a high electrochemical stability.

These attributes give rise to many applications of ionic liquids: They can be used foremost as solvent in synthesis, as electrolyte, as lubricant and as hydraulic fluid. Moreover they serve as phase-transfer catalyst, as extraction medium, as heat-transfer medium, as surface-active substance, as plasticizer, as conductive salt, organic salt or additive in electrochemical cells, as electrolyte, as component in electrolyte formulations, wherein such electrolyte formulation comprising an ionic liquid is preferably used in electrochemical and/or optoelectronic device such as a photovoltaic cell, a light emitting device, an electrochromic or photo-electrochromic device, an electrochemical sensor and/or biosensor, particularly preferred in a dye sensitized solar cell.

Therefore, there is a fundamental need for ionic liquids having a variety of properties which open up additional opportunities for their use. K. B. Dillon et al., J. Chem. Soc, Chem. Commun., 1983, 1089-1090, mentions a trans- PF₂(CN)4 anion, but the cation is not identified.

EP 2 410 601 Al discloses ionic liquids comprising a cyan phosphate-based anion represented by the formula P(CN)_nX6__n with X being halogen. Special emphasis is given to certain specific imidazolium salts of P(CN)₃X₃ with X being F or CI, since all exemplified substances have n = 3 and are trichloro or tri flouro tricyanophosphates. The preparation starts with imidazolium chloride and PC1₅, then reaction with AgCN providing the respective imidazolium P(CN)₃C1₃. In order to obtain the respective imidazolium P(CN)₃F₃, a third step is necessary, that is reaction with AgBF₄ as fluorinating agent. In example 4 even a fourth step follows, addition of imidazolium chloride.

US 2013/0089777 Al disclose a material for use as an electrolyte comprising a lithium salt which comprises the following components (Al) and (B), or which comprises the following components (Al), (A2) and (B):

(Al) a lithium cation;

(A2) an organic cation;

(B) a cyanofluorophosphate anion represented by the formula (1-777):

^"P(CN)_nF₆__n (1-777)

wherein n is an integer of 1 to 5.

Li P(CN)₃F₃ is the only compound disclosed as substance. Its preparation starts with AgCN and PC1₃ providing P(CN)₃, which is converted with LiCl and gaseous Cl₂ to Li P(CN)₃(C1)₃, which is converted with AgBF₄ to Ag P(CN)₃(F)₃, which is converted with Lil to the desired Li P(CN)₃(Cl)₃.

The only two electrolytes disclosed comprise a Li⁺ cation, a trifluorotricyanophosphate anion and optionally a l-ethyl-3-methylimidazolium cation.

JP 2012 009158 A discloses an electrolyte useful in a lithium secondary battery comprising components (Al), (A2) and (B), with (Al) being a Lithium cation, (A2) being an organic cation and (B) being a cyanofluorophosphate -based anion represented by the general formula

P(CN)_nF₆-n, wherein n is an integer of 1 to 5. l-ethyl-3-methylimidazolium trifluorotricyanophosphate is the only compound disclosed as substance. Its preparation is identical with the preparation disclosed in EP 2 410 601 Al and starts with PC1₅ and l-ethyl-3-methylimidazolium chloride, then reaction with AgCN providing l-ethyl-3-methylimidazolium P(CN)3Cl3. In order to obtain the respective imidazolium P(CN)₃F₃, a third step is necessary, that is reaction with AgBF₄ as fluorinating agent, then a fourth step follows, addition of l-ethyl-3-methylimidazolium chloride.

The only one specific electrolyte disclosed contains a Li⁺ cation, a l-ethyl-3- methylimidazolium cation and a trifluorotricyanophosphate anion. JP 2012 248515 A discloses a metal salt useful for an electrode protective film forming agent, the metal salt comprises a component (Al) or a component (A2), and a component (B), (Al) being a monovalent metal cation (excluding a lithium cation), (A2) being a divalent metal cation and (B) being a cyanofluorophosphate type anion represented by the

formula P(CN)_nF₆-_n, wherein n is an integer of 1 to 5.

Only one embodiment is exemplified, which is Ag P(CN)₃F₃. Its preparation is identical with the initial preparation steps disclosed in US 2013/0089777 Al and starts with AgCN and PC1₃ providing P(CN)₃, which is converted with LiCl and gaseous Cl₂ to Li P(CN)₃(C1)₃, which is converted with AgBF₄ to Ag P(CN)₃(F)₃. No example is disclosed for the embodiment component (A2), which is a divalent metal cation.

EP 2 587 580 Al discloses an electrolyte material containing a lithium salt comprising the components (Al-580) and (B-580), or containing the components (Al-580), (A2-580) and (B- 580):

(Al-580) a lithium cation;

(A2-580) an organic cation; and

(B-580) a cyanofluorophosphate anion represented by the following general formula (1-580):

^"P(CN)_nF₆__n (1-580)

wherein n is an integer of 1 to 5.

The only n exemplified is n = 3 in form of the cyanofluorophosphates AgP(CN)₃F₃ and LiP(CN)₃F₃ and in form of the electrolyte material containing a lithium cation, a l-ethyl-3- methylimidazolium cation and a trifluorotricyanophosphate anion. There was a need for a simplified method with high yield and satisfactory purity for the preparation of fluoro cyanide compounds of the 15th group of the periodic table with the anion having the general formula [(Z¹(Q¹)₆__m(CN)_m) ] with Z¹ being P, As, Sb or Bi, Q¹ being

CI or F and m being 1 , 2, 3, 4 or 5. The method should require as few steps as possible. The method should allow also the preparation of compounds with m being 1 , 2, 4 or 5 and not only of compound with m being 3. The method should avoid the use of Cl₂, AgCN of AgBF₄.

Furthermore there was a need for compounds with good properties and performance such as high thermal stability, low melting point, high stability against acids or bases, low viscosity, good electrochemical properties such as large electrochemical window, high and stable efficiency over time, high conductivity, high light fastness, high transparency, good solvent properties and high solubility.

The method should provide stable compounds of said formula which can be used as ionic liquids or as precursors of ionic liquids and can be used e.g. in electrolyte formulations and in electrochemical or optoelectronic devices. These compounds should be able to be disposed of in an environmentally friendly manner after use.

This object is achieved by a method using trimethylsilylcyanide as CN source. No Cl₂, AgCN or AgBF₄ is required. Another advantage is that the reaction does not require an extra solvent. The method has a reduced number of steps compared to the methods known from the prior art. The method allows for the preparation not only of compounds with m = 3, but also for compounds with m = 1 , 2, 4 or 5. The compounds obtained show good performance such as high thermal stability, low melting points, high stability against acids or bases or good electrochemical properties.

In this text, the following meanings are used, if not otherwise stated:

alkyl linear or branched alkyl;

Ci__q alkyl refers to any alkyl residue which contains from 1 to q carbon atoms; for

example Ci_₆ alkyl encompasses inter alia methyl, ethyl, propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethylpropyl), n-hexyl and isohexyl (4-methylpentyl); C₂-_q alkenyl refers to an alkenyl residue which contains from 2 to q carbon atoms and contains at least one double bond, the carbon chain can be linear or branched; for example C₂_₄ alkenyl encompasses inter alia ethenyl, 1-methylethenyl, prop-l-enyl, prop-2-enyl, 2-methylprop-2-enyl and buta-l ,3-dienyl;

C₂__q alkynyl refers to an alkynyl residue which contains from 2 to q carbon atoms and contains at least one triple bond, the carbon chain can be linear or branched; for example C₂_₄ alkynyl encompasses inter alia ethynyl, prop-l-ynyl and prop-2-ynyl;

C₆-io aryl refers to an aryl residue which has from 6 to 10 carbon atoms and is

unsubstituted or substituted by 1 , 2, 3 or 4 identical or different substituents independently from each other selected from the group consisting of Ci_₄ alkyl and Ci_₄ alkoxy; for example C_6-10 aryl encompasses inter alia phenyl, methylphenyl, methoxyphenyl, dimethylphenyl, ethylmethylphenyl, diethylphenyl and naphthyl;

cyclic alkyl or cycloalkyl include cyclo and polycyclo, such as bicyclo or tricyclo,

aliphatic residues;

C3__q cycloalkyl refers to a cycloalkyl group having from 3 to q carbon atoms; for

example C3-10 cycloalkyl encompasses inter alia cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl;

Ci__q alkoxy refers to an linear or branched alkoxy group having from 1 to q carbon atoms; for example Ci_₂o alkoxy encompasses inter alia methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, 1 ,4- dimethylpentyloxy, hexyloxy, heptyloxy, octyloxy, 1 ,5-dimethylhexyloxy, nonyloxy, decyloxy, 4-ethyl- 1 ,5-dimethylhexyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy and eicosyloxy;

alkylene means a linear or branched alkylene group; e.g. propylene, and e.g. propylene can be connected via its C I and C2 carbon atoms (a branched alkylene group), or via its C I and C3 carbon atoms (linear alkylene group);

BMMIm n-Butyl-2-methyl-3-methylimidazolium

n-Butylmethylpyridinium

BMPyrr n-Butylmethylpyrrolidinium

:

BMPip n-Butylmethylpiperidinium

DCM dichloromethane;

EMIm l-ethyl-3-methylimidazolium

eq. molar equivalent;

halide F , CI , Br or I , preferably F , CI or Br , more preferably CI

halogen F, CI, Br or I; preferably F, CI or Br;

HEIm 1-ethylimidazolium

;

IL ionic liquid;

"linear" and "n-" are used synonymously with respect to the respective isomers of alkanes; n-Bu n-Butyl

RT room temperature, it is used synonymously with the expression ambient

temperature;

dec decomposition temperature;

TMSCN (CH₃)₃SiCN, i.e. trimethylsilylcyanide;

"wt%", "% by weight" and "weight-%" are used synonymously and mean percent by weight. The expressions dye sensitized solar cell and photosensitized solar cell are used

synonymously.

SUMMARY OF THE INVENTION Subject of the invention is a method for the preparation of compound of formula (I);

the method comprises a step (Stl) or a step (St3);

step (Stl) comprises a reaction (Real), wherein compound of formula (Al)

[Cat^H^Q¹),)^" ],, (Al) is reacted with trimethylsilylcyanide; step (St3) comprises a reaction (Rea3), wherein compound formula (A3)

is reacted with trimethylsilylcyanide in the presence of compound of formula (I-Cat-n);

(Catⁿ )_tl (AnINORG^q")_t2 Z¹ is selected from the group consisting of P, As, Sb and Bi;

n+ n+

Cat is selected from the group consisting of inorganic cation CatlNORG and organic n+

cation CatORG ;

Q¹ is F or CI;

m is 1, 2, 3, 4 or 5;

n is 1, 2, 3 or 4;

q is 1 or 2;

tl is 1 or 2;

t2 is 1, 2, 3 or 4;

when n is 1 and q is 1, then tl is 1 and t2 is 1;

when n is 2 and q is 1 , then tl is 1 and t2 is 2;

when n is 3 and q is 1, then tl is 1 and t2 is 3;

when n is 4 and q is 1 , then tl is 1 and t2 is 4; when n is 1 and q is 2, then tl is 2 and t2 is 1 ;

when n is 2 and q is 2, then tl is 1 and t2 is 1 ;

when n is 3 and q is 2, then tl is 2 and t2 is 3;

when n is 4 and q is 2, then tl is 1 and t2 is 2;

AnINORG is an anion selected from the group consisting of halide, OH^", CN , OCN , SC , N₃ ^~, sulfate, hydrogensulfate, nitrate, C0₃ ^2", HC0₃ ^", BF₄ ^", PF₆ ^", SbF₆ ^", CF₃S0₃ ^", (CF₃S0₂)₂N^~, (FS0₂)₂N^~, d_₆ alkyl-S0₃ ^", d_₆ alkyl-0-S0₃ ^",

, anions of Ci_₂o monocarboxylic aliphatic acids, mono- and dianions of C₂_₆ dicarboxylic aliphatic acids, anions of benzoic acids, mono- and dianions of phthalic acids, of isophthalic acids and of terephthalic acids, N(CN)₂ ,

C(CN)₃ ^", B(CN)₄ ^", P(CN)₆ ^", Sb(CN)₆ ^", and mixtures thereof;

CatlNORG is a cation selected from the 1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 1 1., 12., 13., 14.,

15. or 16. group of the periodic table, or is a cation from the lanthanides, a cation from the actinides, NH₄ ⁺, H₃0⁺ or H₅0₂ ⁺;

CatORGⁿ⁺ is selected from the group consisting of CatORG-A⁺, CatORG-B⁺, CatORG- C⁺, CatORG-D⁺, CatORG-E⁺, guanidinium and (H₂(R18)N-R16-N(R19)H₂)²⁺;

CatORG-A⁺ is (WR2R3R4R5)⁺,

wherein

W is a nitrogen or phosphorus; and

(i) R2, R3, R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_₂o alkyl, Ci_₂o

perfluoroalkyl, C₃_io cycloalkyl and C₆-io aryl, with the proviso, that at least one of the residues R2, R3, R4 and R5 is not H; or

(ii) R2 and R3 together are a hydrocarbon chain and form together with W a 5- to

7-membered saturated or unsaturated heterocyclic ring, R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_₂o alkyl, Ci_₂₀ perfluoroalkyl, C₃_i₀ cycloalkyl and C_6-1o aryl; or

(iii) R2 and R3 together are a hydrocarbon chain and form together with W, and R4 and R5 together are a hydrocarbon chain and form together with W, independently from each other, 5- to 7-membered saturated or unsaturated heterocyclic rings;

CatORG-B⁺ is (XR6R7R8)⁺,

wherein

X is nitrogen,

R6 and R7 together are a hydrocarbon chain and form together with X a 5- to 7-membered unsaturated heterocyclic ring in which X is connected by a single bond and a double bond to R6 and R7 respectively,

R8 is selected from the group consisting of H, Ci_₂o alkyl, C₂_s alkenyl, Ci_₂o

perfluoroalkyl, C₃_i₀ cycloalkyl or C_6-10 aryl;

CatORG-C⁺ is (YR9R10R1 1)⁺,

wherein

Y is sulphur;

(i) R9, RIO and Rl 1 are identical or different and independently from each other selected from the group consisting of H, Ci_₂o alkyl, Ci_₂o

perfluoroalkyl, C₃_io cycloalkyl and C₆-io aryl; or

(ii) R9 and RIO together are a hydrocarbon chain and form together with Y a 5- to

7-membered saturated or unsaturated ring,

Rl 1 is selected from the group consisting of H, Ci_₂o alkyl, Ci_₂o perfluoroalkyl, C₃_io cycloalkyl and C₆-io aryl;

CatORG-D⁺ is (ZR12R13)⁺,

wherein

Z is oxygen or sulphur;

R12 and R13 together are a hydrocarbon chain and form together with Z a 5- to 7-membered heterocyclic ring in which Z is connected by a single bond and a double bond to R12 and R13 respectively; CatORG-E is a cyclic C_nx alkane or a cyclic C_nx alkene bearing a positive charge, wherein

nx is 3, 5, 7 or 9,

said cyclic C_nx alkene has 1 double bond in case of nx being 3, 2 double bonds in case of nx being 5, 3 double bonds in case of nx being 7, and 4 double bonds in case of nx being 9,

said cyclic C_nx alkane and cyclic C_nx alkene are unsubstituted or substituted by 1 to nx

identical or different substituents independently from each other selected from the group consisting of Ci_₆ alkyl, phenyl, N(R14)R15 and Si(CH₃)₃,

with R14 and R15 are identical or different and independently from each other selected from the group consisting of H and Ci_₆ alkyl; the residues R2, R3, R4, R5, R6, R7, R8, R9, RIO, Rl 1, R12 and R13 are, independently from each other, unsubstituted or, where applicable, substituted by 1, 2, 3, 4, 5 or 6 substituents selected from the group consisting of Ci_₄ alkyl, C₃_i₀ cycloalkyl, C₂_8 alkenyl, phenyl, benzyl, halogen, cyano and Ci_₄ alkoxy; in any of said hydrocarbon chains formed by R2 and R3, by R4 and R5, by R6 and R7, by R9 and R10, and by R12 and R13, 1 or 2 carbon atoms of said hydrocarbon chains can be exchanged for 1 or 2 heteroatoms respectively, said one or two heteroatoms being selected from the group consisting of O, N and S; in case of an exchange for N, this N is unsubstituted or substituted by a residue selected from the group consisting of Ci_s alkyl, C₃_io cycloalkyl, C₂_s alkenyl and Ci_s perfluoroalkyl;

R16 is selected from the group consisting of C₂_s alkylen, C₃_s cycloalkylen, phenylen,

C(H)(phenyl), R17(-0-R17)„i;

R17 is selected from the group consisting of CH₂-CH₂, CH₂-CH₂-CH₂, CH₂-C(H)(CH₃)-

CH₂, CH₂-CH₂-C(H)(CH₃) and CH₂-CH₂-CH₂-CH₂;

R18 and R19 are identical or different and independently from each other selected from the group consisting of H, Ci_s alkyl, C₃_s cycloalkyl, phenyl and benzyl;

nl is an integer from 1 to 20.

DETAILED DESCRIPTION OF THE INVENTION Preferably, Z¹ is P with any of the embodiments disclosed in the specification.

Preferably, n is 1 or 2. In one preferred embodiment, Q¹ is F.

In another preferred embodiment, Q¹ is CI.

In one preferred embodiment, Q¹ is F and compound of formula (I) is prepared by step (Stl). In another preferred embodiment, Q¹ is CI and compound of formula (I) is prepared by step (St3).

Preferably, m is 2, 3, 4 or 5.

In a more preferred embodiment, m is 4 or 5;

in another more embodiment, m is 2, 3 or 4.

In an even more preferred embodiment, m is 4:

In another even more preferred embodiment, m is 2 or 3.

In one more preferred embodiment, in case of reaction (Real), m is 4 or 5 and Q¹ is F.

In another more preferred embodiment, in case of reaction (Rea3), m is 2, 3 or 4 and Q¹ is CI.

In one even more preferred embodiment, in case of reaction (Real), m is 4 and Q¹ is F.

In another even more preferred embodiment, in case of reaction (Rea3), m is 2 or 3 and Q¹ is CI. In an especially preferred embodiment, in case of reaction (Rea3) and in case of Q¹ being CI, m is 3.

When m is 4, then anion [(Z^!(Q Vm(CN)_m)^" ] in formula (I) is preferably [(cis-P(Q¹)₂(CN)₄)^" ]. When m is 4 and Q¹ is F, then anion

] in formula (I) is preferably [(cis-PF₂(CN)₄)^" ]. Preferably, CatINORGⁿ⁺ is a cation selected from the 1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 11.,

12., 13., 14. or 15. group of the periodic table or is a cation from the lanthanides, NH₄ ⁺, H₃0⁺ or H₅0₂ ⁺;

more preferably, CatINORGⁿ⁺ is a cation selected from the 1., 2., 4., 5., 6., 7., 8., 9., 10., 11., 12., 13., 14. or 15. group of the periodic table or is a cation from the lanthanides, NH₄ ⁺,

H₃0⁺ or H₅0₂ ⁺;

even more preferably, CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺,

Rb⁺, Cs⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ti⁴⁺, Ti³⁺, Zr⁴⁺, Zr³⁺, Hf⁴*, Hf³⁺, V⁴⁺, V³⁺, V²⁺, Nb⁴⁺, Ta⁴⁺, Cr³⁺, Mo⁴⁺, Mo³⁺, Mo²⁺, W⁴⁺, W³⁺, W²⁺, Mn⁴⁺, Mn³⁺, Mn²⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Ru⁴⁺, Ru³⁺, Ru²⁺, Os⁴⁺, Os³⁺, Os²⁺, Co⁴⁺, Co³⁺, Co²⁺, Rh⁴⁺, Rh³⁺, Ir⁴⁺, Ir³⁺, Ni⁴⁺, Ni³⁺,

Ni²⁺, Pd⁴⁺, Pd³⁺, Pd²⁺, Pt⁴⁺, Pt³⁺, Pt²⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, Ag⁴⁺, Ag³⁺, Ag²⁺, Ag⁺, Au³⁺, Au²⁺, Au⁺, Zn²⁺, Zn⁺, Cd²⁺, Cd⁺, Hg²⁺, Hg⁺, B³⁺, Al³⁺, Ga³⁺, Ga⁺, In³⁺, In⁺, Tl³⁺, Tl⁺, Ge⁴⁺,Ge²⁺, Sn⁴⁺,Sn²⁺, Pb⁴⁺, Pb²⁺, As³⁺, Sb³⁺, Bi³⁺, Bi¹⁺, La³⁺, Nb³⁺, Sm³⁺, Eu³⁺, Gd³⁺, NH₄ ⁺, H₃0⁺ and H₅0₂ ⁺;

especially, CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺,

Ti⁴⁺, Ti³⁺, Zr⁴⁺, Zr³⁺, V⁴⁺, V³⁺, V²⁺, Cr³⁺, Mo⁴⁺, Mo³⁺, Mo²⁺, W⁴⁺, W³⁺, W²⁺, Mn⁴⁺, Mn³⁺, Mn²⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Ru⁴⁺, Ru³⁺, Ru²⁺, Co⁴⁺, Co³⁺, Co²⁺, Rh⁴⁺, Rh³⁺, Ir⁴⁺, Ir³⁺, Ni⁴⁺, Ni³⁺, Ni²⁺, Pd⁴⁺, Pd³⁺, Pd²⁺, Pt⁴⁺, Pt³⁺, Pt²⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, Ag⁴⁺, Ag³⁺, Ag²⁺, Ag⁺, Zn²⁺, Zn⁺, Al³⁺, Ga³⁺, Ga⁺, In³⁺, In⁺, Sn⁴⁺,Sn²⁺, Pb⁴⁺, Pb²⁺, Sb³⁺, Nb³⁺, Sm³⁺, Eu³⁺, Gd³⁺, NH₄ ⁺, H₃0⁺ and H₅0₂ ⁺;

more especially, CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, Mg²⁺,

Ca²⁺, Ti⁴⁺, V⁴⁺, V³⁺, V²⁺, Cr³⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Co⁴⁺, Co³⁺, Co²⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, Ag²⁺, Ag⁺, Zn²⁺, Zn⁺, Al³⁺, Sn⁴⁺,Sn²⁺, Pb⁴⁺, Pb²⁺, Sb³⁺, Eu³⁺, Gd³⁺, NH₄ ⁺, H₃0⁺ and H₅0₂ ⁺;

even more especially, CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺,

Λ τ4+ ₇·3+ ^ ₃+ 4+ ₃+ 4+ ^ 3+ 4+ ^ 3+

Mg , Ca , Τι , V , V , Cr , Fe , Fe , Fe , Co , Co , Co , Cu , Cu , Cu , Cu ,

Ag⁺, Ζη²⁺, Al³⁺, Sn⁴⁺,Sn²⁺, Pb⁴⁺, Pb²⁺, Gd³⁺, NH₄ ⁺, H₃0⁺ and H₅0₂ ⁺.

In one particular embodiment,

CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, Ag⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Zn²⁺, Cu²⁺, H₃0⁺ and H₅0₂ ⁺; preferably, CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺,

NH₄ ⁺, Ag⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺ , H₃0⁺ and H₅0₂ ⁺;

more preferably, CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, NH₄ ⁺,

Ag⁺, Mg²⁺, Ca²⁺, H₃0⁺ and H₅0₂ ⁺;

NH₄ ⁺, Ag⁺, H₃0⁺ and H₅0₂ ⁺;

especially, CatINORGⁿ is selected from the group consisting of Li⁺, Na⁺, K⁺, Ag⁺, H₃0⁺ and

H₅0₂ ⁺;

in one more especial embodiment, CatINORGⁿ⁺ is selected from the group consisting of Li⁺, K⁺, Ag⁺, H₃0⁺ and H₅0₂ ⁺;

in another more especial embodiment, CatINORGⁿ is selected from the group consisting of

Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Zn²⁺, Cu²⁺, H₃0⁺ and H₅0₂ ⁺;

particularly, CatlNORG is selected from the group consisting of Li , K , Mg , Ca , Zn ,

Cu²⁺, H₃0⁺ and H₅0₂ ⁺;

more particularly, CatINORGⁿ⁺ is selected from the group consisting of Li⁺, K⁺, Mg²⁺, Ca²⁺, H₃0⁺ and H₅0₂ ⁺.

In another particular embodiment,

CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, NH₄ ⁺, Ag⁺, Mg²⁺, Ca²⁺, Zn²⁺, Cu²⁺, H₃0⁺ and H₅0₂ ⁺;

more in particular, CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, NH₄ ⁺,

Ag⁺, Mg²⁺, Ca²⁺, Zn²⁺, H₃0⁺ and H₅0₂ ⁺;

even more in particular, CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, Ag⁺, Mg²⁺, Zn²⁺, H₃0⁺ and H₅0₂ ⁺;

especially in particular, CatINORGⁿ⁺ is selected from the group consisting of Li⁺, K⁺, Ag⁺, Mg²⁺, Zn²⁺, H₃0⁺ and H₅0₂ ⁺.

Preferably, n in CatlnORG The term "where applicable" in the definition of CatORGⁿ means, that any of the optional substituents of the residues R2 to R13 requires a respective site, and e.g. in case of R2 being a perfluorinated side chain no respective site is available any more for a substituent. Preferably, CatORGⁿ contains a heteroatom selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen;

more preferably, CatORGⁿ contains a heteroatom selected from the group consisting of

nitrogen and phosphorus. Preferably,

R16 is selected from the group consisting of C₂_6 alkylen, C₅_₆ cycloalkylen, phenylen,

C(H)(phenyl), R17(-0-R17)_ni;

R17 is selected from the group consisting of CH₂-CH₂, CH₂-CH₂-CH₂ and

R18 and R19 are identical or different and independently from each other selected from the group consisting of H, Ci_₄ alkyl, C₅-6 cycloalkyl, phenyl and benzyl; nl is an integer from 1 to 10;

more preferably,

R16 is selected from the group consisting of C₂_₄ alkylen, C₆ cycloalkylen, phenylen, C(H)(phenyl), R17(-0-R17)„i;

R17 is selected from the group consisting of CH₂-CH₂ and CH₂-CH₂-CH₂;

R18 and R19 are identical and selected from the group consisting of H, Ci_₄ alkyl,

C₅-6 cycloalkyl, phenyl and benzyl;

nl is an integer from 1 to 6;

even more preferably, for n being 2 CatORGⁿ⁺ is (H₂(R18)N-R16-N(Rl 9)H₂)²⁺;

R16 is selected from the group consisting of C₂_₄ alkylen, phenylen and C(H)(phenyl); R18 and R19 are identical and selected from the group consisting of H, Ci_₄ alkyl, C₅-6 cycloalkyl, phenyl and benzyl;

especially, when n is 2, then CatORG is (H₃N-CH₂-CH₂-NH₃)²⁺.

In another preferred embodiment, when n is 1, then CatORG is selected from the group consisting of cation CatORG- A⁺, CatORG-B⁺, CatORG-C⁺, CatORG-D⁺ and CatORG-E⁺; CatORG-A is (WR2R3R4R5) ,

wherein

W is a nitrogen or phosphorus;

perfluoroalkyl, C₃_i₀ cycloalkyl and C_6-10 aryl, with the proviso, that at least one of the residues R2, R3, R4 and R5 is not H; or

(ii) R2 and R3 together with W form a 5- to 7-membered saturated or unsaturated ring, R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_₂₀ alkyl, Ci_₂₀ perfluoroalkyl, C₃_i₀ cycloalkyl and C_6-10 aryl; or

(iii) R2 and R3 together with W and R4 and R5 together with W form, independently from each other, a 5- to 7-membered saturated or unsaturated ring;

CatORG-B⁺ is (XR6R7R8)⁺,

wherein

X is nitrogen,

R6 and R7 together with X form a 5- to 7-membered unsaturated ring in which X formally has one single bond and one double bond to R6 and R7 respectively,

R8 is selected from the group consisting of Ci_₂₀ alkyl, Ci_₂₀ perfluoroalkyl, C₃_i₀

cycloalkyl or C₆-io aryl;

CatORG-C⁺ is (YR9R10R11)⁺,

wherein

Y is sulphur;

(i) R9, RIO and Rl 1 are identical or different and independently from each other selected from the group consisting of Ci_₂o alkyl, Ci_₂o perfluoroalkyl, C3-10 cycloalkyl and C₆-io aryl; or

(ii) R9 and RIO together with Y form a 5- to 7-membered saturated or unsaturated ring, Rl 1 is selected from the group consisting of Ci_₂o alkyl, Ci_₂o perfluoroalkyl, C_3-10 cycloalkyl and C₆-io aryl;

CatORG-D is (ZR12R13)⁺, wherein

Z is oxygen or sulphur;

R12 and R13 together with Z form a 5- to 7-membered ring in which Z formally has one

single bond and one double bond to R12 and R13 respectively;

CatORG-E⁺ is a cyclic C₃_9 alkane or a cyclic C₃_9 alkene bearing a positive charge; in case of a cyclic C₃_₉ alkene, CatORG-E⁺ has 1 , 2 or 3 double bonds; the residues R2, R3, R4, R5, R6, R7, R8, R9, RIO, Rl 1 , R12 and R13 are, independently from each other, unsubstituted or, where applicable, substituted by 1 , 2 or 3 substituents selected from the group consisting of halogen, cyano and Ci_₄ alkoxy; the rings formed by R2 and R3 together with W, R4 and R5 together with W, R6 and R7

together with X, R9 and RIO together with Y and R12 and R13 together with Z contain no, 1 or 2 further heteroatoms, the heteroatoms being selected from the group consisting of O, N and S; and wherein any further heteroatom N can be substituted by Ci_₈ alkyl or Ci_8 perfluoroalkyl.

Preferably, n in CatORGⁿ⁺ is 1. In another preferred embodiment, CatORGⁿ is selected from the group consisting of

ammonium, phosphonium, sulfonium, pyrrolidinium, pyrrolinium, pyrrolium, pyrazolium, pyrazolinium, imidazolium, imidazolinium, triazolium, oxazolium, thiazolium, piperidinium, piperazinium, morpholinium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, 1 ,3-dioxolium, pyrylium and thiopyrylium, quinoxalinium, indolinium, indolium, cyclopropenylium, 1 ,2,3-triphenylcyclopropenylium, tri-tert- butylcyclopropenylium, 1 ,2,3-tris(diethylamino)cyclopropenylium, 1 ,2,3- tris(trimethylsilyl)cyclopropenylium and tropylium, 1 ,2,3, 4,5, 6,7-heptaphenylcyclohepta- 2,4,6-trien- 1 -ylium.

In another preferred embodiment, CatORGⁿ is selected from the group consisting of

ammonium, phosphonium, sulfonium, pyrrolidinium, pyrrolinium, pyrrolium, pyrazolium, imidazolium, triazolium, oxazolium, thiazolium, piperidinium, piperazinium, morpholinium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, 1 ,3-dioxolium, pyrylium and thiopyrylium, cyclopropenylium, 1 ,2,3-triphenylcyclopropenylium, tri-tert- butylcyclopropenylium, 1 ,2,3-tris(diethylamino)cyclopropenylium, 1 ,2,3- tris(trimethylsilyl)cyclopropenylium and tropylium, 1 ,2,3, 4,5, 6,7-heptaphenylcyclohepta- 2,4,6-trien- 1 -ylium.

In a particular embodiment, CatORG-E⁺ is selected from the group consisting of

cyclopropenylium, 1 ,2,3-triphenylcyclopropenylium, tri-tert-butylcyclopropenylium,

1 ,2,3-tris(diethylamino)cyclopropenylium, 1 ,2,3-tris(trimethylsilyl)cyclopropenylium and tropylium, 1 ,2,3, 4,5, 6,7-heptaphenylcyclohepta-2,4,6-trien-l -ylium.

In a particular embodiment, CatORG is selected from the group consisting of

More preferably, CatORG is selected from the group consisting of

[N(R20)(R21)(R22)R23]⁺ and [P(R20)(R21)(R22)R23]⁺; wherein

R20 is Ci_2o alkyl or C3-10 cycloalkyl;

R21 , R22 and R23 are identical or different and independently selected from the group

consisting of H and Ci_₂o alkyl; preferably,

R20 is Ci_i4 alkyl or C5-8 cycloalkyl;

consisting of H and Ci_i₄ alkyl; more preferably,

R20 is Ci_8 alkyl or C₅_₇ cycloalkyl;

Pv21 , R22 and R23 are identical or different and independently selected from the group consisting of H and Ci_s alkyl.

Even more referably, CatORGⁿ⁺ is selected from the group consisting of

, , [NH(C₂H₅)₃]⁺, [NH(C₄H₉)₃]⁺, [N(C₂H₅)₄]⁺, [N(C₄H₉)₄]⁺,

[P(C₂H₅)₄]⁺, [P(C₄H₉)₄]⁺ and [P(C₆H₁₃)₃(C₁₄H₂₉)]⁺;

,

, [NH(C₂H₅)₃]⁺, [NH(C₄H₉)₃]⁺, [N(C₂H₅)₄]⁺,

[N(C₄H₉)₄]⁺, [P(C₂H₅)₄]⁺, and [P(C₄H₉)₄]

,n+ .

In another more preferable embodiment, CatORG is selected from the group consisting

, [NH(C₂H₅)₃]⁺, [NH(C₄H₉)₃]⁺, [N(C₂H₅)₄]⁺ and [N(C₄H₉)₄]⁺ and optionally

[P(C₂H₅)₄]⁺ and optionally [P(C₄H₉)₄]⁺;

wherein

R20, R22 is Ci_₂o alkyl or C₃_io cycloalkyl;

R21 is H and Ci_₂o alkyl;

preferably,

R20, R22 is C_1-14 alkyl or C₅_s cycloalkyl;

R21 is H and C i_i ₄ alkyl;

more preferably,

R20, R22 is Ci_s alkyl or C5-7 cycloalkyl;

R21 is H and Ci_8 alkyl; even more preferably,

R20 and R22 are independently from each other methyl, ethyl, butyl or cyclohexyl, and

R21 is H, methyl or ethyl.

In particular, Cat is a cation (Cat-Part 1); cation (Cat-Parti) is CatINORGⁿ⁺ or CatORGⁿ⁺,

I 2 2 2 2 with CatlNORG selected from the group consisting of Li , Na , K , Mg , Ca , Zn , Cu , Ag⁺, H₃0⁺ and H₅0₂ ⁺, preferably of Li⁺, K⁺, Ag⁺, H₃0⁺ and H₅0₂ ⁺; and

_s , R20 \ R21 , , [NH(C₂H₅)₃]

[NH(C₄H₉)₃]⁺, [N(C₂H₅)₄]⁺ and [N(C₄H₉)₄]⁺ and optionally [P(C₄H₉)₄]⁺;

R20 is methyl, ethyl, propyl, butyl or cyclohexyl;

R21 is H, methyl or ethyl;

R22 is H or methyl; more in particular, Cat is a cation (Cat-Part2); cation (Cat-Part2) is CatINORGⁿ⁺ or CatORGⁿ⁺, with CatlNORG selected from the group consisting of Li , Na , K , Mg , Ca , Zn , Cu , Ag⁺, H₃0⁺ and H₅0₂ ⁺, preferably of Li⁺, K⁺, Ag⁺, H₃0⁺ and H₅0₂ ⁺; and with CatORGⁿ⁺ selected from the group consisting of

_? [ H(C₂H₅)₃]⁺, [NH(C₄H₉)₃f , [N(C₂H₅)₄] and [N(C₄H₉)₄] and optionally [P(C₄H₉)₄]⁺; even more in particular, Cat is a cation (Cat-Part3); cation (Cat-Part3) is CatINORGⁿ⁺ or CatORGⁿ⁺,

I 2 2 2 with CatlNORG selected from the group consisting of Li , Na , K , Mg , Ca , Zn , Cu ,

Ag , H₃0 and H₅0₂ , preferably of Li , K , Ag , H₃0 and H₅0₂ ; and

with CatORG^" selected from the roup consisting of

_? [ H(C₂H₅)₃]⁺, [NH(n-Bu)₃]⁺, [N(C₂H₅)₄]⁺ and [N(n-Bu)₄]⁺ and optionally [P(n-Bu)₄]⁺; n+ .

very more in particular, Cat is a cation (Cat-Part4); cation (Cat-Part4) is CatINORGⁿ⁺ or CatORGⁿ⁺, with CatlNORG selected from the group consisting of Li , Na , K , Mg , Ca , Zn , Cu Ag⁺, H₃0⁺ and H₅0₂ ⁺, preferably of Li⁺, K⁺, Ag⁺, H₃0⁺ and H₅0₂ ⁺; and

with CatORGⁿ⁺ selected from the group consisting of

, [NH(C₂H₅)₃f and [N(n-Bu)₄] and optionally [P(n-Bu)₄] very, very more in particular, Cat is a cation (Cat-Part5);

cation (Cat-Part5) is CatINORGⁿ⁺ or CatORGⁿ⁺,

with CatlNORG selected from the group consisting of Li , Na , K , Mg , Ca , Zn , Cu

Ag⁺, H₃0⁺ and H₅0₂ ^†, preferably of Li^†, K^†, Ag^†, H₃0^† and H₅0₂ ^†; and

with CatORG selected from the roup consisting of

.

n+

Another particular preferred embodiment of Cat is a cation (Cat-Part6),

cation (Cat-Part6) is selected from the group consisting of Li , Na , K , Mg , Ca , Zn ,

Cu²⁺, Ag⁺, H₃0⁺, H₅(V

, [N(n- Bu)₄]⁺, [P(n-Bu)₄]⁺, [N(n-Octyl)₄]⁺, [P(n-Octyl)₄]⁺, 1,3-dimethylimidazolium,

1 -ethyl-3 -methylimidazolium, 1 -propyl-3 -methylimidazolium, 1 -allyl-3 - methylimidazolium, l-methyl-3-hexylimidazolium, 1-ethylimidazolium and l-butyl-2,3- dimethylimidazolium.

Another particular preferred embodiment of Cat is a cation (Cat-Part7),

cation (Cat-Part7) is selected from the group consisting of Li , Na , K , Mg , Ca , Zn , Cu²⁺, Ag⁺, H₃0⁺, H₅0₂ ⁺, [N(n-Bu)₄]⁺, [P(n-Bu)₄]⁺, [N(n-Octyl)₄]⁺, [P(n-Octyl)₄]⁺,

+

/ \

3 n-L ₄i i<) i_?3_di_methylimidazolium, 1 -ethyl-3 -methylimidazolium, 1 -propyl-3 - methylimidazolium, 1 -allyl-3 -methylimidazolium, l-methyl-3-hexylimidazolium and 1- butyl-2,3-dimethylimidazolium.

Another particular preferred embodiment of Cat is a cation (Cat-Part8),

cation (Cat-Part8) is selected from the group consisting of Li⁺, K⁺, Mg²⁺, Ca²⁺, [N(n-Bu)₄]

+

/ \

[P(n-Bu)₄]⁺, ³ n-L^Hg ^ i_?3_di_methylimidazolium, 1 -ethyl-3 -methylimidazolium and 1 -propyl-3 -methylimidazolium.

Another particular preferred embodiment of Cat is a cation (Cat-Part9),

I 2"!" 2"!" I cation (Cat-Part9) is selected from the group consisting of Na , Mg , Ca , Zn , Cu , [N(n-

Octyl)₄]⁺, [P(n-Octyl)₄]⁺, _? i_?3.dimethylimidazolium, l-propyl-3- methylimidazolium, 1 -allyl-3 -methylimidazolium and l-methyl-3-hexylimidazolium.

Another particular preferred embodiment of Cat is a cation (Cat-PartlO), catio -PartlO) is selected from the group consisting of Li , K ,

[N(n-Bu)₄]⁺, [P(n-Bu)₄f,

l-ethyl-3-methylimidazolium, 1-ethylimidazolium and l-butyl-2,3-dimethylimidazolium.

In another preferred embodiment, compound of formula (I) is a compound (COMP-Neg-I), with compound (COMP-Neg-I) having the definition of compound of formula (I) as defined above, also with all the embodiments of compound of formula (I), and with the proviso, that compound (COMP-Neg-I) is none of the compounds selected from the group consisting of [Et₄N⁺] [trans-PF₂(CN)₄ ] and [Ag⁺] [trans-PF₂(CN)₄ ] and optionally compound of formula (NIPP);

compound of formula (NIPP) is selected from the group consisting of

1 -butyl-3-methylimidazolium trichlorotricyanophosphate,

1 -butyl-2,3-dimethylimidazolium trichlorotricyanophosphate,

1 -butyl-3 -methylimidazolium trifluorotricyanophosphate, 1 -ethyl-3 -methylimidazolium trichlorotricyanophosphate and 1 -ethyl-3 -methylimidazolium trifluorotricyanophosphate.

In one more preferred embodiment, compound of formula (I) is a compound (COMP-Neg-II), with compound (COMP-Neg-II) having the definition of compound (COMP-Neg-I) as defined above, and

with the proviso, that compound (COMP-Neg-II) is none of the compounds selected from the group consisting of [Et N⁺] [PF₂(CN)₄ ] and [Ag⁺] [PF₂(CN)₄ ] and optionally compound of formula (NIPP).

In another more preferred embodiment, compound of formula (I) is a compound (COMP-

Neg-III), with compound (COMP-Neg-III) having the definition of compound (COMP- Neg-I) or of compound (COMP-Neg-II) as defined above, and with the proviso, that the anion of compound of formula (I) is not [trans-PF₂(CN)4 ] and optionally compound of formula (I) is also not compound of formula (NIPP).

In another more preferred embodiment, compound of formula (I) is a compound (COMP- Neg-IV), with compound (COMP-Neg-IV) having the definition of compound (COMP- Neg-I) or of compound (COMP-Neg-II) or of compound (COMP-Neg-III) as defined above, and

n+ _{+ +}

with the proviso, that Cat in compound of formula (I) is neither Et₄N nor Ag and

optionally compound of formula (I) is also not compound of formula (NIPP).

Even more preferably, compound of formula (I) is compound (COMP-Pos-I),

compound (COMP-Pos-I) is selected from the group consisting of compound of formula (la), compound of formula (lb), compound of formula (Ic), compound of formula (Id), compound of formula (Ie), compound of formula (If) and compound of formula (Ig);

[Catⁿ⁺] [(cis-PF₂(CN)₄)^" ]„ (la)

[Catⁿ⁺] [(PF!(CN)₅)^" ]_n (lb)

[Catⁿ⁺] [(PF₄(CN)₂)^" ]_n (Ic)

[Catⁿ⁺] [(PF₅(CN))^" ]„ (Id)

[Catⁿ⁺] [(PC1₂(CN)₄)^" ]„ (Ie)

[Catⁿ⁺] [(PC1₃(CN)₃)^" ]_n (if)

[Catⁿ⁺] [(PC1₄(CN)₂)^" ]„ (ig) in one preferred embodiment, compound (COMP-Pos-I) is selected from the group consisting of compound of formula (la) and compound of formula (lb); in another preferred embodiment, compound (COMP-Pos-I) is selected from the group

consisting of compound of formula (lb), compound of formula (Ic), compound of formula (Id), compound of formula (Ie), compound of formula (If) and compound of formula (Ig); in a more preferred embodiment, compound (COMP-Pos-I) is compound of formula (la);

Cat and n are as defined above, also with all their embodiments,

n+

preferably Cat is cation (Cat-Parti);

n+

more preferably Cat is cation (Cat-Part2);

n+

even more preferably Cat is cation (Cat-Part3);

n+

especially Cat is cation (Cat-Part4);

n+

more especially Cat is cation (Cat-Part5). Especially, compound of formula (I) is compound (COMP-Pos-I), also with all the

embodiments of compound (COMP-Pos-I), and with one or more of the provisos defined with respect of compound (COMP-Neg-I), compound (COMP-Neg-II), compound (COMP-Neg-III) and compound (COMP-Neg-IV).

In one particular emcodiment, compound of formula (I) is compound (COMP-Pos-II),

compound (COMP-Pos-II) is compound of formula (la), wherein

n+

Cat is selected from the group consisting of cation cation (Cat-Part6), cation (Cat-Part7), cation (Cat-Part8), cation (Cat-Part9) and cation (Cat-PartlO),

with compound of formula (la), cation (Cat-Part6), cation (Cat-Part7), cation (Cat-Part8), cation (Cat-Part9) and cation (Cat-PartlO) as defined above.

In another particular emcodiment, compound of formula (I) is compound (COMP-Pos-III), compound (COMP-Pos-III) is compound of formula (lb), wherein

n+

Cat is selected from the group consisting of cation (Cat-Part6), cation (Cat-Part7), cation (Cat-Part8), cation (Cat-Part9) and cation (Cat-Parti 0),

Special embodiment of compound of formula (I) is compound (GROUP -II), compound

+ - 2+

(GPvOUP-II) is selected from the group consisting of Li [(cis-PF₂(CN)₄) ], Mg [(cis-PF₂(CN)₄)^" ]₂, Zn²⁺ [(cis-PF₂(CN)₄)^" ]₂, Ca²⁺ [(cis-PF₂(CN)₄)^" ]₂, [H₃0][cis- PF₂(CN)₄], [H₅0₂][cis-PF₂(CN)₄], [N(n-Bu)₄]⁺ [(cis-PF₂(CN)₄)^" ], [P(n-Bu)₄]⁺ [(cis-

PF₂(CN)₄)^" ],

[_Cis-PF₂(CN)₄] , 1,3-dimethylimidazolium [(cis-PF₂(CN)₄)^' ], l-ethyl-3-methylimidazolium [(cis-PF₂(CN)₄) ], l-propyl-3-methylimidazolium

[(cis-PF₂(CN)₄)^" ], [H₃0][cis-PF₂(CN)₄], Mg[cis-PF₂(CN)₄]₂ * 4H₂0,

Zn[cis-PF₂(CN)₄]₂ * 2H₂0, [H₅0₂][cis-PF₂(CN)₄] and mixtures thereof.

Other special embodiments of compound of formula (I) is compound (GROUP-III),

+ - 2^ compound (GROUP-III) is selected from the group consisting of Li [(PF(CN)₅) ], Mg [(PF(CN)₅)^"]₂, Zn²⁺ [(PF(CN)₅)^"]₂, Ca²⁺ [(PF(CN)₅)^"]₂, [N(n-Bu)₄]⁺ [(PF(CN)₅)^"], [P(n-

Bu)₄]⁺ [(PF(CN)₅)^"],

[(PF(CN)₅)^"], 1,3-dimethylimidazolium [(PF(CN)₅) ], l-ethyl-3-methylimidazolium [(PF(CN)₅) ], l-propyl-3-methylimidazolium [(PF(CN)₅) ] and mixtures thereof.

Even more in particular, compound of formula (I) is compound (GROUP), compound

(GROUP) is selected from the group consisting of compound of formula (1), compound of formula (la), compound of formula (lb), compound of formula (2), compound of formula (3), compound of formula (4), compound of formula (5), compound of formula (6), compound of formula (7), compound of formula (8), compound of formula (9), compound of formula (10), compound of formula (11), compound of formula (12), compound of formula (13), compound of formula (14), compound of formula (14a), compound of formula (14b), compound of formula (15), compound of formula (15a), compound of formula (15b), compound of formula (17), compound of formula (18), compound of formula (18a), compound of formula (18b), compound of formula (19), compound of formula (20), compound of formula (21), compound of formula (22), compound of formula (23), compound of formula (24), compound of formula (25), and mixtures thereof.

[(n-Bu)₄N][cis-PF₂(CN)₄] (1)

[(n-Bu)₄N][PF₂(CN)₄], mixture of cis and trans (la)

[(n-Bu)₄N] [trans-PF₂(CN)₄] (lb)

Ag[cis-PF₂(CN)₄] (2)

K[cis-PF₂(CN)₄] (3)

Li[cis-PF₂(CN)₄] (4)

[Et₃HN][ cis-PF₂(CN)₄] (6)

[cis-PF₂(CN)₄] (?)

-C₄H₉ [ci_s.pF₂(CN)₄] (8)

[ci_s.pF₂(CN)₄] (9) C₂H₅ [cis-PF₂(CN)₄] (10)

[(n-Bu)₄P][cis-PF₂(CN)₄] (12)

[(n-Bu)₄N][PF₅(CN)] (13)

[(n-Bu)₄N][cis-PF₄(CN)₂] (14)

[(n-Bu)₄N] [PF₄(CN)₂] , mixture of cis and trans (14a)

[(n-Bu)₄N][trans-PF₄(CN)₂] (14b)

[(n-Bu)₄N][mer-PF₃(CN)₃] (15)

[(n-Bu)₄N][PF₃(CN)₃], mixture of fac and mer (15a)

[(n-Bu)₄N][fac-PF₃(CN)₃] (15b)

[(n-Bu)₄N][trans-PCl₂(CN)₄] (17)

[(n-Bu)₄N][PCl₃(CN)₃] ], mixture of fac and mer (18)

[(n-Bu)₄N][fac-PCl₃(CN)₃] (18a)

[(n-Bu)₄N][mer-PCl₃(CN)₃] (18b)

[(n-Bu)₄N][trans-PCl₄(CN)₂] (19) [(n-Bu)₄N] [cis-PCl₄(CN)₂] (20)

[(n-Bu)₄N][PF(CN)₅] (21)

[H₃0][cis-PF₂(CN)₄] (22)

Mg[cis-PF₂(CN)₄]₂ * 4H₂0 (23)

Zn[cis-PF₂(CN)₄]₂ * 2H₂0 (24)

[H₅0₂][cis-PF₂(CN)₄] (25)

Further subject of the invention is compound of formula (I), wherein compound of formula (I) is any of the above defined compounds or groups of compounds, preferably selected from the group consisting of compound (COMP-Pos-I), compound (COMP-Pos-II), compound (COMP-Pos-III), compound (Group-II), compound (Group-Ill) and compound

(GROUP),

with compound (COMP-Pos-I), compound (COMP-Pos-II), compound (COMP-Pos-III), compound (Group-II), compound (Group-Ill) and compound (GROUP) as defined above, also with all their embodiments;

preferably compound (COMP-Pos-I), compound (COMP-Pos-II), compound (COMP-Pos- III), compound (Group-II), compound (Group-Ill) and compound (GROUP) have been prepared according to the method as defined above, also with all the embodiments of the method.

Preferably, from 1 to 20 mol equivalents, more preferably 4 to 20 mol equivalents, even more preferably from 6 to 15 mol equivalents, of trimethylsilylcyanide are used in reaction (Real), the mol equivalents being based on the molar amount of compound of formula (Al).

The reaction temperatures of reaction (Real) is preferably from 80 to 250°C, more preferably from 150 to 250°C, more preferably from 175 to 225°C, even more preferably 180 to 210°C. Reaction (Real) can be done in a closed system and at the pressure caused by the chosen temperature.

The reaction time of reaction (Real) is preferably from 30 min to 96 h, more preferably from 1 h to 72 h, even more preferably from 2 h to 48 h.

Preferably, reaction (Real) is done under inert atmosphere. Preferably, the inert atmosphere is achieved by the use if an inert gas preferably selected from the group consisting of argon, another noble gas, lower boiling alkane, nitrogen and mixtures thereof.

The lower boiling alkane is preferably a Ci_₃ alkane, i.e. methane, ethane or propane.

After the reaction, compound of formula (I) can be isolated by standard methods such as evaporation of volatile components, extraction, washing, drying, concentration,

crystallization, chromatography and any combination thereof, which are known per se to the person skilled in the art.

Preferably, after the reaction the reaction product is treated with hydrogen peroxide, preferably with aqueous hydrogen peroxide. More preferably for isolation, the reaction product is mixed with aqueous hydrogen peroxide to provide a mixture (M).

Preferably, the concentration of the aqueous hydrogen peroxide is from 10 to 40 wt% hydrogen peroxide, the wt% based on the total weight of the aqueous hydrogen peroxide. Preferably, from 1 to 30 mol equivalents, more preferably from 1 to 20 mol equivalents, of hydrogen peroxide are used, the mol equivalents being based on the molar amount of compound of formula (Al).

Preferably mixture (M) is stirred for 5 min to 12 h, more preferably for 10 min to 6 h.

Preferably mixture (M) is stirred at a temperature (M), temperature (M) is preferably from ambient temperature to 100°C. After treatment with hydrogen peroxide, mixture (M) is preferably filtrated. The residue of the filtration is preferably washed with a solvent (WASH), solvent (WASH) is preferably water. The residue is preferably extracted with a solvent (EXTRACT); solvent (EXTRACT) is preferably acetonitrile, to provide a solution (EXTRACT).

Any drying of an organic phase, e.g. the solution (EXTRACT) obtained after extraction with solvent (EXTRACT), is preferably done with Na₂S0₄, K₂C0₃, CaCl₂ or MgS0₄.

Any isolation from a solution, e.g. from solution (EXTRACT), is preferably done by evaporation of the solvent.

Further preferred embodiments for purification are reversed phase column chromatography and dissolution and treatment of the solution with charcoal and filtration.

Preferably, the method for the preparation of compound of formula (I) comprises a step (St2), step (St2) is done after step (Stl) or after step (St3);

step (St2) comprises a reaction (Rea2), reaction (Rea2) is a metathesis reaction wherein cation n+ n+

Cat in compound of formula (I) is exchanged for a cation different from Cat ;

with compound of formula (I) having been prepared in step (Stl) or in step (St3);

n+

with step (Stl), step (St3), Cat compound of formula (I) as defined above, also with all their embodiments.

Preferably, reaction (Rea2) provides for the preparation of a compound of formula (I-Cat-r);

[Cat- ⁺] [(Z^!(Q Vm(CN)_m)^" ]_r (I-Cat-r) r+ n+ n+

Cat-r is selected from the group consisting of CatlNORG and CatORG and is

n+

different from Cat ;

r is 1, 2, 3 or 4; j j n+ n+

with Z , Q , m, CatlNORG and CatORG as defined above, also with all their embodiments. n+ r+

Preferably, in reaction (Rea2) Cat is exchanged for Cat-r from compound of formula

(I-Cat-n-r);

(Cat-r^r+)_tl (AnINORG^q")t2 (I-Cat-n-r) r+ q- Cat-r , r, tl, t2, AnINORG and q are as defined above, also with all their embodiments; wherein

when r is 1 and q is 1, then tl is 1 and t2 is 1;

when r is 2 and q is 1 , then tl is 1 and t2 is 2;

when r is 3 and q is 1, then tl is 1 and t2 is 3;

when r is 4 and q is 1 , then tl is 1 and t2 is 4;

when r is 1 and q is 2, then tl is 2 and t2 is 1 ;

when r is 2 and q is 2, then tl is 1 and t2 is 1 ;

when r is 3 and q is 2, then tl is 2 and t2 is 3;

when r is 4 and q is 2, then tl is 1 and t2 is 2.

Reaction (Rea2) is a metathesis reaction, also called a salt-exchange reaction. In a metathesis reaction such as reaction (Rea2) a first cation in a first salt is exchanged for a second cation, said second cation coming from a second salt.

Preferably, AnINORG^q is an anion selected from the group consisting of halide, OH^", CN^~, sulfate, hydrogensulfate, nitrate, C0₃ ^2", HC0₃ ^", BF₄ ^", PF₆ ^", CF₃S0₃ ^", (CF₃S0₂)₂N^~, (FS0₂)₂N^~, H₃C-S0₃ ^~, H₃C-CH₂-S0₃ ^~, H₃C-0-S0₃ ^~, H₃C-CH₂-0-S0₃ ^~, acetate, oleate, fumarate, maleate, oxalate, benzoate, N(CN)₂ , and mixtures thereof; more preferably, AnINORG^q is an anion selected from the group consisting of Br , CI , OH^", GST, sulfate, hydrogensulfate, C0₃ ² , HC0₃ , acetate, and mixtures thereof; even more preferably, AnINORG is an anion selected from the group consisting of CI , OH^", GST, sulfate, hydrogensulfate, CO3² , HCO3 , acetate, and mixtures thereof.

In another preferred embodiment, AnINORG^ is an anion selected from the group consisting of halide, OH^", CN^~, OCN , SCN^~, N₃ ^~, sulfate, hydrogensulfate, nitrate, C0₃ ^2", HC0₃ ^", BF₄ ^", PF₆ ^", SbF₆ ^", CF₃S0₃ ^", (CF₃S0₂)₂N^~, (FS0₂)₂N^~, Ci_₆ alkyl-S0₃ ^", Ci_₆ alkyl-0-S0₃ ^",

, anions of Ci_₂o monocarboxylic aliphatic acids, anions of C₂_₆ dicarboxylic aliphatic acids, benzoate, phthalates, N(CN)₂ , C(CN)₃ B(CN)₄ ^", P(CN)₆ ^", Sb(CN)₆ ^", and mixtures thereof. Preferably, r is 1 or 2.

In case of reaction (Rea2), preferably a compound of formula (I-Cat-r) with Cat-r being CatORGⁿ is prepared by exchange of a Catⁿ being a CatINORGⁿ in compound of formula (I) for a CatORGⁿ⁺.

Said CatORGⁿ is provided in reaction (Rea2) preferably in form of a compound of formula (I-CatORG)

(CatORGⁿ⁺)q(AnINORG^q")_n (I-CatORG) wherein

Catⁿ⁺, n, CatORGⁿ⁺, CatINORGⁿ⁺, q and AnINORG^q are as defined above, also with all their embodiments. n+ r+ Preferably, in reaction (Rea2) the cation different from Cat , that is preferably Cat-r , is n+

present in at least such a molar amount relative to the molar amount of Cat as required for a stoichiometric exchange of said two cations; more preferably, compound of formula (I) and compound of formula (I-Cat-n-r) are present in n+

at least such a molar amount relative to each other, that Cat is stoichiometrically

r+

exchanged for Cat-r .

Even more preferably, the molar amount of compound of formula (I-Cat-n-r) is such, that

r+

from 1 to 1.5, even more preferably 1 to 1.2, required equivalents of Cat-r relative to the equivalents of Catⁿ are present.

The reaction temperatures of reaction (Rea2) is preferably from 0 to 250 °C, more preferably from 10 to 200 °C, even more preferably from 10 to 150 °C, especially from 10 to 100°C, more especially from 10 to 50°C.

The reaction (Rea2) is preferably carried out in a solvent (Sol2), solvent (Sol2) is preferably selected from the group consisting of water, DCM, ethyl acetate, C₅_i₀ alkane, and mixtures thereof.

C₅_io alkane is preferably pentane, hexane or heptane.

In a more preferred embodiment, reaction (Rea2) is done in DCM or in a biphasic solvent system of water and DCM.

As an alternative, the reaction can also be carried out in the absence of a solvent or in a solvent in which the inorganic salt formed as side product is sparingly soluble or insoluble. As a further alternative, it is also possible to carry out the reaction in an aqueous solution using an ion exchanger loaded with the desired cation Catⁿ .

The amount of solvent is preferably from 2 to 40 fold, more preferably from 3 to 20 fold, of the weight of compound of formula (I).

Reaction (Rea2) can be done in a closed system and at the pressure caused by the chosen temperature.

The reaction time of reaction (Rea2) is preferably from 15 min to 96 h, more preferably from 15 min to 48 h, even more preferably from 15 min to 24 h. Preferably, reaction (Rea2) is done under inert atmosphere. Preferably, the inert atmosphere is achieved by the use if an inert gas preferably selected from the group consisting of argon, another noble gas, lower boiling alkane, nitrogen and mixtures thereof.

Subsequent to reaction (Rea2) there can be a further metathesis reaction or further metathesis reactions.

After reaction (Rea2), compound of formula (I) can be isolated from the reaction mixture by standard methods such as filtration, evaporation of volatile components, extraction, washing, drying, concentration, crystallization, chromatography and any combination thereof, which are known per se to the person skilled in the art.

For example, when reaction (Rea2) was done in a biphasic solvent system of water and DCM, the aqueous and organic phases are separated, the organic phase is preferably washed, preferably with water, then preferably dried, preferably with Na₂S0₄, K₂C0₃, CaCl₂ or MgS0₄, and finally evaporated.

Or as another example, when reaction (Rea2) was done in DCM and a suspension was formed, filtration and evaporation of the solvent will isolate the product.

Preferably, from 1 to 20 mol equivalents, more preferably from 4 to 20 mol equivalents, even more preferably from 6 to 15 mol equivalents, of trimethylsilylcyanide are used in reaction (Rea3), the mol equivalents being based on the molar amount of compound of formula (A3).

The reaction temperatures of reaction (Rea3) is preferably from -50 to 80°C, more preferably from -40 to 60°C, more preferably from -30 to 40°C.

Reaction (Rea3) can be done in a closed system and at the pressure caused by the chosen temperature.

The reaction time of reaction (Rea3) is preferably from 30 min to 96 h, more preferably from 1 h to 72 h, even more preferably from 2 h to 48 h. Preferably, reaction (Rea3) is done under inert atmosphere. Preferably, the inert atmosphere is achieved by the use if an inert gas preferably selected from the group consisting of argon, another noble gas, lower boiling alkane, nitrogen and mixtures thereof.

After the reaction (Rea3), compound of formula (I) can be isolated by standard methods such as evaporation of volatile components, extraction, washing, drying, concentration, crystallization, chromatography and any combination thereof, which are known per se to the person skilled in the art.

It is possible to treat the reaction product after the reaction with hydrogen peroxide, preferably with aqueous hydrogen peroxide.

Preferably, the reaction product is mixed with aqueous hydrogen peroxide to provide a mixture (M3).

Preferably, the concentration of the aqueous hydrogen peroxide is from 10 to 40 wt% hydrogen peroxide, the wt% based on the total weight of the aqueous hydrogen peroxide.

Preferably, from 1 to 30 mol equivalents, more preferably from 1 to 20 mol equivalents, of hydrogen peroxide are used, the mol equivalents being based on the molar amount of compound of formula (A3).

Preferably mixture (M3) is stirred for 5 min to 12 h, more preferably for 10 min to 6 h.

Preferably mixture (M3) is stirred at a temperature (M3), temperature (M3) is preferably from ambient temperature to 100°C.

After treatment with hydrogen peroxide, mixture (M3) is preferably filtrated. The residue of the filtration is preferably washed with a solvent (WASH3), solvent (WASH3) is preferably water.

The residue is preferably extracted with a solvent (EXTRACT3); solvent (EXTRACT3) is preferably acetonitrile, to provide a solution (EXTRACT3). Any drying of an organic phase, e.g. the solution (EXTRACT3) obtained after extraction with solvent (EXTRACT3), is preferably done with Na₂S0₄, K₂C0₃, CaCl₂ or MgS0₄.

Any isolation from a solution, e.g. from solution (EXTRACT3), is preferably done by evaporation of the solvent.

Further preferred embodiments for purification are reversed phase column chromatography and dissolution and treatment of the solution with charcoal and filtration. In an embodiment of the invention, preferably when Q¹ is CI, step (St2) is done after step (St3), and compound of formula (I-Cat-r) of step (St2) is a compound of formula (I), which has been prepared in step (St3). n+

Compounds of formula (Al) are commercially available depending on the cation Cat , e.g. [(n-Bu₄)N][PF₆] and K[PF₆] are commercially available. Other compounds of formula (Al) n+ _{+ +}

with cations Cat different from K and (n-Bu₄)N , and which are not commercially available, can be prepared by conventional metathesis reaction, i.e. substitution of the respective cation K⁺ or (n-Bu₄)N⁺ against another cation.

Compounds of formula (A3) are commercially available and can be prepared according to or in analogy to known methods.

Further subject of the invention is the use of compound of formula (I), wherein compound of formula (I) is any of the above defined compounds or groups of compounds, preferably selected from the group consisting of compound (COMP-Pos-I), compound (COMP-Pos- II), compound (COMP-Pos-III), compound (Group-II), compound (Group-Ill) and compound (GROUP),

with compound (COMP-Pos-I), compound (COMP-Pos-II), compound (COMP-Pos-III), compound (Group-II), compound (Group-Ill) and compound (GROUP)as defined above, also with all their embodiments;

preferably compound (COMP-Pos-I), compound (COMP-Pos-II), compound (COMP-Pos- III), compound (Group-II), compound (Group-Ill) and compound (GROUP) have been prepared according to the method as defined above, also with all the embodiments of the method; preferably the use of compound of formula (I) with Catⁿ being CatORGⁿ , with CatORGⁿ as defined above, also with all its embodiments;

as solvent, preferably as solvent in organic and organic synthesis; as phase-transfer catalyst, as extractant, as heat-transfer medium, as surface-active substance, as plasticizer, as conductive salt, organic salt or additive in electrochemical cells, further as electrolyte; as lubricant, as hydraulic fluid or as component in electrolyte formulations;

further their use in electrochemical and/or optoelectronic devices, especially in electrolytres or electrolyte formulations which are used in electrochemical and/or optoelectronic devices.

Said electrolyte formulations comprising a compound of formula (I), preferably a compound of formula (I) with Catⁿ being CatORGⁿ , with CatORGⁿ as defined above, also with all its embodiments, are preferably used in electrochemical and/or optoelectronic devices; wherein the electrochemical and/or optoelectronic devices are preferably selected from the group consisting of batteries, capacitors, supercapacitors, electrochemical cells, photovoltaic cell, light emitting device, electrochromic or photo-electrochromic device, electrochemical sensor and/or biosensor, and dye sensitized solar cell, particularly preferred compound of formula (I) is used in battareies and in dye sensitized solar cells; preferably any of these compounds of formula (I) have been prepared according to the method as defined above, also with all the embodiments of the method.

In the case of the use of compounds of formula (I) as solvents, these are suitable in any type of reaction known to the person skilled in the art, for example for transition-metal- or enzyme-catalyzed reactions, such as, for example, hydroformylation reactions,

oligomerisation reactions, esterifications or isomerisations, where the said list is not exhaustive.

When used as extractant, compound of formula (I) can be employed to separate off reaction products, but also to separate off impurities, depending on the solubility of the respective component in the ionic liquid. In addition, the ionic liquids may also serve as separation media in the separation of a plurality of components, for example in the distillative separation of a plurality of components of a mixture. Further possible applications for compounds of formula (I) are the use as plasticizer in polymer materials and as conductive salt or additive in various electrochemical cells and applications, for example in galvanic cells, in capacitors or in fuel cells. Further fields of applications of compounds of formula (I), according to this invention, are their use as solvents for carbohydrate containing solids, in particular biopolymers and derivatives or degradation products thereof.

Further, compound of formula (I) can be used as lubricants or hydraulic fluids, preferably in machines such as compressors, pumps or hydraulic devices.

A further field of application is the field of particle or nanomaterial synthesis where these ionic liquids can act as medium or additive. Electrolyte formulations comprising a compound of formula (I), preferably a compound of formula (I) with Catⁿ being CatORGⁿ , can be preferably used in electrochemical and/or optoelectronic devices such as batteries, preferably primary batteries and secondary batteries, further capacitors, supercapacitors or electrochemical cells, optionally also in combination with further conductive salts, additives and/or solvents. Preferred batteries are lithium batteries or lithium-ion batteries. A preferred capacitor is a lithium-ion capacitor.

Electrolyte formulations comprising a compound of formula (I), preferably a compound of formula (I) with Catⁿ being CatORGⁿ , can be preferably used in electrochemical and/or optoelectronic devices such as a photovoltaic cell, a light emitting device, an electrochromic or photo-electrochromic device, an electrochemical sensor and/or biosensor, and a dye sensitized solar cell, particularly preferred in a dye sensitized solar cell.

Electrolyte formulations comprising a compound of formula (I), preferably a compound of formula (I) with Catⁿ being CatORGⁿ , can used used in addition or as an alternatives to already known electrolyte formulations. They show especially in the field of electrolyte formulations of dye sensitized solar cells increased power conversion efficiency particularly under low temperature. The advantage of the use of compounds of formula (I) is their low viscosity, and subsequently the smaller Nernst diffusion resistance of the oxidant species, especially at lower temperature.

Compound of formula (I) exhibit interesting melting points, thermal and electrochemical stability, viscosity, polarity and solubility in water or in organic solvents.

Compounds of formula (I) are halogen-free, which makes inexpensive and environmentally friendly disposal possible, for example by incineration, and they have low corrosivity towards metals, which simplifies their use and storage. Further subject of the invention is

(a) an electrolyte formulation (ElFormul) which comprises the compound of formula (I), and

(b) an electrochemical or an optoelectronic device (ElDev) which comprises the electrolyte formulation (ElFormul);

wherein compound of formula (I) is any of the above defined compounds or groups of

compounds, preferably selected from the group consisting of compound (COMP-Pos-I), compound (COMP-Pos-II), compound (COMP-Pos-III), compound (Group-II), compound (Group-Ill) and compound (GROUP),

An electrolyte formulation (ElFormul) can comprise in addition to compound of formula (I) a solvent (ElSolv).

Solvent (ElSolv) is preferably an organic solvent, which can reduce the viscosity, can increase the ionic conductivity and the electric pemittivity.

Solvent (ElSolv) is, for example, selected from the group consisting of

ester carbonates, preferably ethylene carbonate and propylene carbonate,

lactones, preferably gamma-butyrolactone, gamma-valerolactone and delta-valerolactone, ethers, preferably 1 ,2-dimethoxyethane, diethoxyethane, ethylene glycol dimethyl ether, polyethylene glycol dimethyl ether and 1,4-dioxane,

alcohols, preferably ethanol, ethylene glycol monomethyl ether and polyethylene glycol monoalkyl ether,

glycols, preferably ethylene glycol, propylene glycol and polyethylene glycol,

tetrahydrofurans, preferably tetrahydrofuran and 2-methyltetrahydrofuran,

nitriles, preferably acetonitrile, glutarodinitrile, propionitrile, valeronitrile,

methoxyacetonitrile and benzonitrile,

carboxylic esters, preferably methyl acetate, ethyl acetate and ethyl propionate,

phosphate triesters, preferably trimethyl phosphate and triethyl phosphate,

heterocyclic compounds, preferably N-methylpyrrolidone, 2-methyl-l,3-dioxolane, N- butylbenzimidazole and sulfolane,

nonprotonic organic solvents, preferably dimethyl sulfoxide, formamide, N,N- dimethylformamide and nitromethane,

and mixtures thereof;

more preferably, solvent (ElSolv) is selected from the group consisting of ethylene carbonate, propylene carbonate, tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile,

glutarodinitrile, propionitrile, valeronitrile, methoxyacetonitrile, trimethyl phosphate, triethyl phosphate, N-methylpyrrolidone, 2-methyl-l,3-dioxolane, N-butylbenzimidazole, sulfolane, dimethyl sulfoxide, formamide, Ν,Ν-dimethylformamide, nitromethane, and mixtures thereof;

even more preferably, solvent (ElSolv) is selected from the group consisting of propylene carbonate, acetonitrile, propionitrile, N-methylpyrrolidone, 2-methyl-l,3-dioxolane, N- butylbenzimidazole, sulfolane, dimethyl sulfoxide, Ν,Ν-dimethylformamide, and mixtures thereof;

especially solvent (ElSolv) is selected from group consisting of sulfolane,

N-butylbenzimidazole and acetonitrile.

An electrolyte formulation (ElFormul) can also comprise water. An electrolyte formulation (ElFormul) containing water can further enhance the energy conversion efficiency of a photosensitized solar cell.

An electrolyte formulation (ElFormul) can also comprise electrically insulating particles, semiconductor particles, and electroconductive particles. An electrolyte formulation (ElFormul) can also comprise a salt (ElSalt), salt (ElSalt) is preferably not an ionic liquid. Salt (ElSalt) is more preferably an inorganic iodide, even more preferably an iodide of a metal ion of the first main group of the periodic table, especially salt (ElSalt) is selected from the group consisting of Lil, Nal and KI.

Further subject of the invention is an electrolyte formulation (ElFormulMix-la) comprising the electrolyte formulation (ElFormul) and a compound (IonLiqu),

wherein

compound (IonLiqu) is a salt or an ionic liquid which is not a compound of formula (I);

with the electrolyte formulation (ElFormul) as defined above, also with all its embodiments; preferably electrolyte formulation (ElFormulMix-la) comprises also a salt (ElSalt), with salt (ElSalt) as defined above, also with its embodiments.

Preferably, compound (IonLiqu) in the electrolyte formulation (ElFormulMix-la) is

compound of formula (I-Cat-n), with compound of formula (I-Cat-n) as defined above, also with all its embodiments.

In one more preferable embodiment, compound (IonLiqu) in the electrolyte formulation

(ElFormulMix-la) is compound of formula (I -IonLiqu);

(CatORGⁿ⁺)_tl (AnINORG^q")_t2 (I-IonLiqu) wherein

n+

CatORG , AnINORG, n, q, tl and t2 are as defined above, also with all their embodiments; even more preferably, compound (IonLiqu) is a compound of formula (I-IonLiqu), wherein AnINORG^q is an anion selected from the group consisting of halide, GST, OCN , SCN^~,

N₃ ^~, sulfate, hydrogensulfate, BF₄ ^", PF₆ ^", SbF₆ ^", CF₃S0₃ ^", (CF₃S0₂)₂N^~, (FS0₂)₂N^~, anions of Ci_₂o monocarboxylic aliphatic acids, N(CN)₂ , C(CN)₃ , B(CN)₄ , P(CN)₆ ,

Sb(CN)₆ , and mixtures thereof; and

n+

with CatORG being as defined above, also with all its embodiments;

especially, compound (IonLiqu) is a compound of formula (I-IonLiqu), wherein AnINORG^q is an anion selected from the group consisting of Br , I , SCN^~, BF₄ , PF₆ , CF₃SO₃ , (CF₃S0₂)₂N , (FS0₂)₂N , anions of Ci_₂o monocarboxylic aliphatic acids, N(CN)₂ ^", C(CN)₃ ^", B(CN)₄ ^", and mixtures thereof and

CatORG is selected from the group consisting of

_s l _?3- dimethylimidazolium, 1 -ethyl-3-methylimidazolium, 1 -propyl-3-methylimidazolium, 1 -allyl-3 -methylimidazolium, 1 -methyl-3 -hexylimidazolium, 1 -ethylimidazolium, l-butyl-2,3-dimethylimidazolium and mixture thereof;

more especially, compound (IonLiqu) is a compound of formula (I-IonLiqu), wherein

AnINORG^q is an anion selected from the group consisting of I , SCN ^~, (CF₃S0₂)₂N , (FS0₂)₂N^~, N(CN)₂ ^", C(CN)₃ ^", B(CN)₄ ^", and mixtures thereof; and

+

CatORG^" is selected from the group consisting of ^ ¹³ n-^tig ^

dimethylimidazolium, 1 -ethyl-3 -methylimidazolium, 1 -propyl-3 -methylimidazolium, 1 -allyl-3 -methylimidazolium, 1 -methyl-3 -hexyl imidazolium, 1-ethylimidazolium, l-butyl-2,3-dimethylimidazolium and mixture thereof;

even more especially, compound (IonLiqu) is a compound of formula (I-IonLiqu), wherein

AnINORG^q is an anion selected from the group consisting of I , SCN^~, (CF₃S0₂)₂N , (FS0₂)₂N^~, N(CN)₂ ^", C(CN)₃ ^", B(CN)₄ ^", and mixtures thereof; and

+

CatORG is selected from the group consisting of ³ 4 9 , \ ,3- dimethylimidazolium, 1 -ethyl-3 -methylimidazolium, 1 -propyl-3 -methylimidazolium, 1 -allyl-3 -methylimidazolium, 1 -methyl-3 -hexyl imidazolium and mixture thereof; in one particular embodiment, compound (IonLiqu) is a compound of formula (I-IonLiqu), wherein AnINORG^q is an anion selected from the group consisting of I , SCN ^~, (CF₃S0₂)₂N , (FS0₂)₂N^~, N(CN)₂ ^", C(CN)₃ ^", B(CN)₄ ^", and mixtures thereof; and

+

CatORG is ^{3 11} 4^H9 _? l-ethyl-3-methylimidazolium or l-propyl-3- methylimidazolium;

in another particular embodiment, compound (IonLiqu) is selected from the group consisting

+ of ^, 4' iodide, 1 ,3-dimethylimidazolium iodide, l-ethyl-3-methylimidazolium iodide, l-propyl-3-methylimidazolium iodide, l-allyl-3-methylimidazolium iodide, l-methyl-3-hexyl imidazolium iodide and mixtures thereof.

In another more preferable embodiment, compound (IonLiqu) in the electrolyte formulation (ElFormulMix-la) is compound of formula (II-IonLiqu);

(CatINORGⁿ )_tl (AnINORG^q")_t2 (II-IonLiqu) wherein

n+

CatlNORG , AnINORG, q, tl and t2 are as defined above, also with all their

embodiments;

even more preferably, compound (IonLiqu) is a compound of formula (I-IonLiqu), wherein AnINORG^q is an anion selected from the group consisting of halide, GST, OCN , N₃ ^~, sulfate, hydrogensulfate, BF₄ ^", PF₆ ^", SbF₆ ^", CF₃S0₃ ^~, (CF₃S0₂)₂N^~, (FS0₂)₂N^~, anions of Ci_₂₀ monocarboxylic aliphatic acids, N(CN)₂ , C(CN)₃ , B(CN)₄ , P(CN)₆

Sb(CN)₆ , and mixtures thereof; and

n+

with CatlNORG being as defined above, also with all its embodiments;

especially, compound (IonLiqu) is a compound of formula (I-IonLiqu), wherein AnINORG^q is an anion selected from the group consisting of BF₄ , PF₆ , CF₃SO₃ , (CF₃S02)2N , (FSC^N , anions of Ci_2o monocarboxylic aliphatic acids, N(CN)2 , C(CN)3 , B(CN)₄ , and mixtures thereof; and

CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, Ag⁺, Mg²⁺, Zn²⁺, Ca²⁺, Ba²⁺, H₃0⁺ and H₅0₂ ⁺;

AnINORG^q is an anion selected from the group consisting of BF₄ , PF₆ , (CF₃S0₂)₂N , (FS0₂)₂N^", N(CN)₂ ^", C(CN)₃ ^", B(CN)₄ ^", and mixtures thereof; and

I _|_ _|_ _|_ _{2 2}

CatlNORG is selected from the group consisting of Li , Na , K , Mg , Zn , Ca , H₃0⁺ and H₅0₂ ⁺;

AnINORG^q is an anion selected from the group consisting of PF₆ , (CF₃S0₂)₂N ,

(FS0₂)₂N^~ and B(CN)₄ ^"; and

CatINORGⁿ is selected from the group consisting of Li⁺, Na⁺, K⁺, Mg²⁺, Zn²⁺, H₃0⁺ and H₅0₂ ⁺.

In yet another more preferable embodiment, compound (IonLiqu) in the electrolyte

formulation (ElFormulMix-la) is compound of formula (I-Cat-n),

with compound of formula (I-Cat-n) as defined above, also with all its embodiments;

wherein

Cat is selected from the group consisting of CatORG-B⁺,

, Li⁺, Na⁺, K⁺, Mg²⁺ and Zn²⁺;

AnINORG^q is selected from the group consisting of PF₆ ^", (CF₃S0₂)₂N^", (FS0₂)₂N^~ and

B(CN)₄ ^";

tl is 1;

t2 is 1 or 2;

when n is 1 and q is 1, then tl is 1 and t2 is 1;

when n is 2 and q is 1 , then tl is 1 and t2 is 2; with CatORG-B as defined above, also with all its embodiments;

n+

preferably CatORG-B is selected from the group consisting of 1,3-dimethylimidazolium, 1- ethy -methylimidazolium, 1 -propyl-3 -methylimidazolium, 1 -allyl-3 -methylimidazolium, l-methyl-3-hexyl imidazolium, 1-ethylimidazolium, l-butyl-2,3-dimethylimidazolium and mixture thereof;

n+

more preferably with CatORG-B being l-ethyl-3 -methylimidazolium or

1 -propyl-3 -methylimidazolium. Further subject of the invention is an electrolyte formulation (ElFormulMix-lb) comprising the electrolyte formulation (ElFormul) and a redox couple (RedOxCoup),

wherein

redox couple (RedOxCoup) is selected from the group consisting of Br /Br₂, 1 /I₃,

SCN7SCN₂, SeCN^~/SeCN₂ and bipyridine cobalt (III/II); preferably, redox couple (RedOxCoup) is I /I3 or bipyridine cobalt (III/II);

with the electrolyte formulation (ElFormul) as defined above, also with all its embodiments.

Further subject of the invention is an electrolyte formulation (ElFormulMix-2) comprising the electrolyte formulation (ElFormul), a compound (IonLiqu) and a redox couple

(RedOxCoup);

with the electrolyte formulation (ElFormul), a compound (IonLiqu) and a redox couple

(RedOxCoup) as defined above, also with all their embodiments;

preferably, compound (IonLiqu) is compound of formula (I-IonLiqu);

with compound of formula (I-IonLiqu) as defined above, also with all its embodiments; in one more preferable embodiment, electrolyte formulation (ElFormulMix-2) comprises also salt (ElSalt);

in another more preferable embodiment, electrolyte formulation (ElFormulMix-2) comprises also solvent (ElSolv);

and in an especial embodiment, electrolyte formulation (ElFormulMix-2) comprises also salt (ElSalt) and solvent (ElSolv);

with salt (ElSalt) and solvent (ElSolv) as defined above, also with all their embodiments. EXAMPLES

Methods

1H, ¹³C, ¹⁹F and ³¹P NMR spectra were recorded on a Bruker AVANCE 300 and Bruker AVANCE 250 instruments in CD₃CN, D₆-DMSO or CD₂C1₂. Chemical shifts are expressed in parts per million referred to TMS in case of 1H and ¹³C, C¹⁹FCl₃ m case of ¹⁹F, and H₃ ³¹P0₄ in case of ³¹P, and coupling constants (J) in Hertz. When a % value for the amount of compounds is stated based on NMR measurement, the % value represents an area-%, the area- % being based on the total area of peaks in the spectrum.

IR-spectra were recorded on a Nicolet 380 FT-IR spectrometer. Measurements were done at room temperature.

RAMAN-spectra were recorded on a LabRAM HR 800 Horiba Jobin YVON. Measurements were done at room temperature.

The C/H/N-analyses were measured on a C/H/N/S-Analysator (Thermoquest Flash EA 1112).

Melting points and temperature of decomposition Td_ec were measured on a DSC 823e from Mettler-Toledo. The calibration was carried out with the melting points of In (156.6 ± 0.3°C) and Zn (419.6 ± 0.7°C) with an heating rate of 5 K per min.

TGA/DSC measurements were conducted on a Setaram Labsys TGA / DSC 1600. The measurements were carried out under argon atmosphare with a heating rate of 5 K per min, corrected via a blank measurement.

Preparation Description (1): Synthesis of [(n-Bu₄)N] [PF₆]

K[PF₆] (2.055 g, 11.2 mmol) was dissolved in 30 ml of H₂0. [(n-Bu₄)N]Br (3.601 g, 11.2 mmol) was dissolved in 30 ml of CH₂C1₂ and added to the aqueous solution of K[PF₆]. After stirring for 24 hours at ambient temperature the phases were separated. The organic phase was washed three times with 10 ml of water dried over anhydrous Na₂C0₃ and filtered. The filtrate was concentrated on a rotary evaporator to obtain a white solid. The obtained solid was dried at 80°C in vacuum for 18 hours. The yield of [(n-Bu₄)N][PF₆] was 3.822 g (88 %, 9.87 mmol). DSC (10 K/min): m.p. = 250°C, T_dec = 388°C

C/H/N Analysis calc. % (found): C 49.60 (49.97), H 9.37 (9.00), N 3.61 (3.61)

1H NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): 0.96 (t, 12H, CH₃), 1.34 (m, 8H,

CH₃-CH₂), 1.59 (m, 8H, CH₂-CH₂N), 3.06 (m, 8H, NCH₂)

¹⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -73.0 (d, 6F, PF₆, ^P-^F) = 706.7 Hz)

³¹P NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -144.6 (sept, IP, PF₆, ^P-^F) = 706.7 Hz)

IR (ATR, 32 scans, v in cm^"1): 2966 (m), 2937 (w), 2879 (w), 1472 (m), 1404 (w), 1386 (w), 1360 (w), 1350 (w), 1319 (w), 1260 (w), 1242 (w), 1165 (w), 1109 (w), 1070 (w), 1035 (w), 931 (w), 880 (m), 829 (s), 738 (m), 555 (s)

Example 2: Synthesis of compound of formula (1)

[(n-Bu)4N][PF₆] (1.381 g, 3.57 mmol), prepared according to Preparation Description (1), and (CH₃)₃SiCN (3.54 g, 35.7 mmol) were filled under argon atmosphere with a residual oxygen content of below 5 ppm and with a residual water content of below 1 ppm into a teflon tube of an autoclave.

The autoclave was placed inside a muffle furnace and heated to 200°C within 30 minutes. The temperature was held for 16.5 h.

After cooling to ambient temperature the obtained black oily reaction mixture was mixed with water (10 ml) and aqueous H₂0₂ (6 ml, 60 mmol, 30 wt%). After stirring at 80°C for 3 h and cooling to ambient temperature the suspension was filtered. The remaining solid was washed two times with water. The remaining solid was extracted with 15 ml of CH₃CN and filtered. The CH₃CN was evaporated on a rotary evaporator. The obtained yellow solid substance was dried at 50°C in vacuum to yield 591 mg (40%, 1.42 mmol) of compound of formula (1). In accordance to ¹⁹F and ³¹P NMR the product contains around 1% impurities of

[(n-Bu)₄N][PF₆__y(CN)_y] with y = 2, 3 and 5. DSC (10 K/min): m.p. = 64°C

C/H/N Analysis calc: % (found): C 57.81 (57.76), H 8.73 (8.78), N 16.85 (16.40)

MS (ESI-TOF): calc. % (found): cation 242.284 (242.285), anion 172.983 (172.983) 1H NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): 0.96 (t, 12H, CH₃), 1.34 (m, 8H,

CH₃-CH₂), 1.59 (m, 8H, CH₂-CH₂N), 3.07 (t, 8H, NCH₂) ¹³C NMR (25 °C, CD₃CN, 250.13 MHz, delta in ppm): 13.8 (s, 4C, CH₃), 20.3 (t, 4C,

CH₃-CH₂), 24.3 (s, 4C, CH₂-CH₂N), 59.3 (t, 4C, NCH₂),

1⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -6.1 (d, 2F, PF₂(CN)₄, ^P-^F) =

729.2 Hz)

3¹P NMR (25°C, CD₃CN, 96.29 MHz, delta in ppm): -269.2 (d, IP, PF₂(CN)₄, ^P-^F) = 729.2 Hz)

IR (ATR, 32 scans, v in cm^"1): 2966 (m), 2938 (m), 2878 (m), 2202 (m), 2193 (m), 1484 (m), 1469 (m), 1380 (m), 1150 (w), 1107 (w), 1065 (w), 1027 (w), 884 (m), 792 (s), 774 (s), 764 (s), 673 (s), 569 (s), 541 (s)

RAMAN (100 mW, 25°C, 4 scans, cm^"1): 2974 (w), 2942 (m), 2880 (w), 2216 (m) 2205 (vs), 2197 (m), 1483 (w), 1473 (m), 1462 (m), 1454 (s), 1326 (m), 1313 (w), 1155 (w), 1136 (m), 1112 (w), 1056 (m), 1040 (w), 1005 (w), 914 (s), 904 (w), 883 (w), 798 (w), 597 (w), 574 (vs), 545 (vw), 524 (w), 473 (m), 436 (w), 402 (w), 393 (m), 305 (vw), 255 (vs), 219 (s)

Compound of formula (1) was obtained from the described evaporation of the CH₃CN on a rotary evaporator and subsequent drying in vacuum at 50°C in form of a powder. In order to obtain crystals suitable for x-ray crystal structure determination, a small amount of the powder was dissolved in a small amount of acetonitrile and the solvent was evaporated by letting the solution stand in an open container without lid overnight. The crystals formed were suitable for x-ray crystal structure determination. The x-ray crystal structure determination revealed cis-configuration of the two fluorine atoms.

Example 3: Synthesis of compound of formula (1)

Example 2 was repeated with the difference that [(n-Bu)₄N][PF₆] (9.521 g, 24.57 mmol) and (CH₃)₃SiCN (22 g, 222 mmol) were used. After extracting the product with CH₃CN and drying the product in vacuum the light brown solid substance was recrystallized from ethanol to give a white solid. After drying in vacuum at 50°C 5.929 g (58%, 14.27 mmol) of compound of formula (1) were isolated.

In accordance to ¹⁹F and ³¹P NMR the product contains around 1% impurities of

[(n-Bu)₄N][PF₆__y(CN)y] with y = 2, 3 and 5.

C/H/N Analysis calc.% (found): C 57.81 (58.13), H 8.73 (8.63), N 16.86 (16.74)

The NMR and IR data are the identical with those in example 2. Example 4: Synthesis of compound of formula (2)

Compound of formula (1) (5.929 g, 14.27 mmol), prepared according to example 3, was dissolved in 120 ml MeOH. This solution was added to a 10% aqueous solution of AgN0₃ (2.449 g, 14.41 mmol) under omission of light. A white precipitate of Ag[PF₂(CN)4] occurred. After 30 min of stirring the solid was filtered and washed three times with 15 ml of water/methanol (1 : 1). After drying the solid in vacuum at 70°C 3.504 g (12.47 mmol, 87 %) of compound of formula (2) were obtained. DSC (10 K/min): T_dec = 184°C

C/H/N Analysis calc.% (found): C 17.10 (17.06), H 0.00 (0.29), N 19.94 (19.37)

¹⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -6.09 (d, 2F, ^(^F-^P) = 731 Hz,

²J(¹⁹F-¹³C) = 38 Hz, ²J(¹⁹F-¹³C) = 66 Hz)

3¹P NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -269.15 (t, IP, ^P-^F) = 732 Hz, ^P-^C) = 144 Hz, ^P-^C) = 220 Hz)

IR (25°C, ATR, 32 scans, v in cm^"1): 2235 (w), 2219 (m), 802 (s), 696 (s), 665 (s), 575 (s), 538 (s)

In order to obtain crystals suitable for x-ray crystal structure determination, a small amount of compound of formula (2) was dissolved in a small amount of acetonitrile and then Et₂0 was allowed to vapor-diffuse into the prepared acetonitrile solution. The crystals formed were suitable for x-ray crystal structure determination. The x-ray crystal structure determination revealed cis-configuration of the two fluorine atoms. Example 5: Synthesis of compound of formula (3)

Compound of formula (2) (2.996 g, 10.67 mmol), prepared according to example 4, were dissolved in 80 ml CH₃CN. A solution of KBr (1.282 g, 10.77 mmol) in 5 ml water was added. A greenish precipitate of AgBr occurred. After 30 min of stirring the AgBr was filtered off. The filtrate was dried on a rotary evaporator. The obtained solid was diluted in 50 ml water and filtered. The aqueous solution was washed two times with 10 ml CH₂C1₂. The aqueous solution was concentrated and fractionally crystallized. After drying 2.015 g (89%, 9.50 mmol) of compound of formula (3) were obtained.

DSC (10 K/min): m.p. = 228°C, T_dec = 250 C/H/N Analysis calc.% (found): C 22.65 (22.46), H 0.00 (0.00), N 26.41 (25.99)

¹³C NMR (25°C, D6-DMSO, 250.13 MHz, delta in ppm): 125.73 (dt, 2C, ^(^C-^P) = 218

Hz, ²J(¹³C-¹⁹F) = 65 Hz), 128.05 (dt, 2C, ^(^C-^P) = 143 Hz, ²J(¹³C-¹⁹F) = 38 Hz)

1⁹F NMR (25°C, D6-DMSO, 300.13 MHz, delta in ppm): -5.79 (d, 2F, ^ ^P) = 731 Hz, 2J(¹⁹F-¹³C) = 38 Hz, ²J(¹⁹F-¹³C) = 65 Hz)

³¹P NMR (25°C, D6-DMSO, 300.13 MHz, delta in ppm): -268.90 (t, IP, ^!J(³¹P-¹⁹F) = 730

Hz, ^P-^C) = 143 Hz, ^P-^C) = 218 Hz)

IR (25°C, ATR, 32 scans, v in cm^"1): 2212 (w), 771 (s), 671 (s), 574 (m), 544 (m)

In order to obtain crystals suitable for x-ray crystal structure determination, a small amount of the powder was dissolved in a small amount of methanol and the solvent was slowly evaporated in an open container without lid. The crystals formed were suitable for x-ray crystal structure determination. The x-ray crystal structure determination revealed cis- configuration of the two fluorine atoms.

Example 6: Synthesis of compound of formula (4)

Compound of formula (2) (0.496 g, 1.77 mmol), prepared according to example 4, was dissolved in 10 ml CH₃CN. A solution of LiBr (0.153 g, 1.77 mmol) in 2 ml water was added. A greenish precipitate of AgBr occurred. After 30 min of stirring the AgBr was filtered off. The filtrate was dried on a rotary evaporator. The obtained solid was diluted in 10 ml water and filtered. The aqueous solution was washed two times with 5 ml CH₂CI₂. After drying 284 mg (89%, 1.58 mmol) of compound of formula (4) were obtained.

DSC (10 K/min): T_dec = 334°C

C/H/N Analysis calc.% (found): C 26.69 (26.78), H 0.00 (0.14), N 31.13 (30.97)

¹³C NMR (25°C, CD₃CN, 250.13 MHz, delta in ppm): 125.78 (dt, 2C, ^!J(¹³C-³¹P) = 220 Hz,

²J(¹³C-¹⁹F) = 66 Hz), 128.37 (dt, 2C, ^!J(¹³C-³¹P) = 144 Hz, ²J(¹³C-¹⁹F) = 38 Hz)

1⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -0.82 (d, 2F, ^!J(¹⁹F-³¹P) = 730 Hz, 2J(¹⁹F-¹³C) = 38 Hz, ²J(¹⁹F-¹³C) = 65 Hz)

3¹P NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -263.74 (t, IP, ^!J(³¹P-¹⁹F) = 730 Hz, !J(³¹P-¹³C) = 144 Hz, ^!J(³¹P-¹³C) = 220 Hz)

IR (25°C, ATR, 32 scans, v in cm^"1): 2226 (w), 809 (s), 665 (s), 581 (m), 544 (m) In order to obtain crystals suitable for x-ray crystal structure determination, a small amount of the powder was dissolved in a small amount of absolute THF and the solvent was slowly evaporated. The crystals formed were suitable for x-ray crystal structure determination. The x-ray crystal structure determination revealed cis-configuration of the two fluorine atoms.

Example 7: Synthesis of compound of formula (5)

Compound of formula (3) (1.531 g, 7.22 mmol), prepared according to example 5, was dissolved in 70 ml water. An aqueous solution of EMImBr (1.394 g, 7.30 mmol) in 30 ml water was added. After 30 min of stirring at ambient temperature the product was extracted three times with 20 ml CH₂CI₂. The combined organic phases were dried over anhydrous Na₂S0₄ and filtered. After evaporating the solvent and drying the colourless liquid in vacuum at 60°C 1.950 g (6.86 mmol, 95 %) of compound of formula (5) were obtained. The liquid showed low viscosity. DSC (10 K/min): m.p.= -32°C, T_dec = 20FC

C/H/N Analysis calc.% (found): C 42.26 (42.12), H 3.90 (4.09), N 29.57 (28.96)

1H NMR (25°C, CD₃CN, 250.13 MHz, delta in ppm): 1.46 (t, 3H, CH₃), 3.82 (s, 3H, NCH₃), 4.16 (q, 2H, NCH₂), 7.32 (m, 1H, EtNCH), 7.37 (m, 1H, MeNCH), 8.39 (s, 1H, NCHN) ¹³C NMR (25 °C, CD₃CN, 250.13 MHz, delta in ppm): 15.49 (s, 1C, NCH₂-CH₃), 36.56 (s, 1C, NCH₃), 45.38 (s, 1C, NCH₂), 122.68 (s, 1C, EtNCH), 124.15 (s, 1C, MeNCH),

127.17 (dt, 2C, ^(^C-^P) = 218 Hz, ²J(¹³C-¹⁹F) = 66 Hz), 129.77 (dt, 2C, ^(^C-^P) = 144 Hz, ²J(¹³C-¹⁹F) = 38 Hz), 137.28 (br, 1C, NCHN)

1⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -6.10 (d, 2F, ^ ^P) = 731 Hz, 2J(¹⁹F-¹³C) = 38 Hz, ²J(¹⁹F-¹³C) = 66 Hz)

3¹P NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -269.10 (t, IP, ^P-^F) = 731 Hz, 2J(³¹P-¹³C) = 144 Hz, ²J(³¹P-¹³C) = 218 Hz)

IR (25°C, ATR, 32 scans, v in cm^"1): 3157 (w), 3120 (w), 2991 (w), 2966 (w), 2947 (w), 2202 (m), 2195 (m), 1574 (w), 1470 (w), 1452 (w), 1429 (w), 1390 (w), 1358 (w), 1336 (w), 1165 (s), 1109 (w), 1088 (w), 1032 (w), 959 (w), 777 (s), 765 (s), 702 (w), 667 (s), 646 (s), 621 (s), 569 (s), 542 (s)

Example 8: Synthesis of compound of formula (12)

Compound of formula (3) (0.212 g, 1.00 mmol), prepared according to example 5, was dissolved in 15 ml water. A solution of [(n-Bu)₄P]Br (0.339 g, 1.00 mmol) in 15 ml CH₂C1₂ was added. After 60 min of stirring at ambient temperature the product was extracted three times with 15 ml CH₂CI₂. The combined organic phases were washed two times with water and dried over anhydrous Na₂S0₄ and filtered. After evaporating the solvent and drying of the product in vacuum at 50°C compound of formula (12) was obtained as a white solid (391 mg, 0.90 mmol, 90 %).

DSC (10 K/min): m.p.= 75°C, T_dec = 289°C

C/H/N Analysis calc.% (found): C 55.54 (55.89), H 8.39 (8.36), N 12.96 (12.64)

1H NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): 0.95 (t, 12H, CH₃), 1.48 (m, 16H, CH₂- CH₂), 2.05 (m, 8H, PCH₂)

¹³C NMR (25 °C, CD₃CN, 300.13 MHz, delta in ppm): 13.62 (s, 4C, CH₃), 19.00 (d, 4C, PCH₂, ^(^C-^P) = 48 Hz), 23.94 (d, 4C, CH₃-CH₂, ³J(¹³C-³¹P) = 5 Hz), 24.58 (d, 4C, PCH₂-CH₂, ²J(¹³C-³¹P) = 15Hz)

1⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -6.04 (d, 2F, ^ ^P) = 731 Hz) ³¹P NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): 33.72 (s, IP, Bu₄P), -269.13 (t, IP, PF₂(CN)₄, ^P-^F) = 730 Hz)

IR (25°C, ATR, 32 scans, v in cm^"1): 2963 (m), 2935 (m), 2876 (m), 2201 (w), 2193 (w), 1465 (m), 1451 (w), 1407 (w), 1383 (w), 1349 (w), 1314 (w), 1283 (w), 1236 (w), 1223 (w), 1206 (w), 1189 (w), 1099 (m), 1082 (w), 1051 (w), 1005 (w), 969 (w), 920 (w), 908 (m), 866 (w), 794 (s), 776 (s), 718 (m), 672 (s), 570 (m), 542 (m)

Example 9: Synthesis of compound of formula (6)

Example 8 was repeated with the difference that compound of formula (3) (0.423 g, 2.00 mmol), prepared according to example 5, and Et₃HNCl (0.275 g, 2.00 mmol) were used. Compound of formula (6) was obtained as a white solid (0.355 g, 65 %, 1.29 mmol).

DSC (10 K/min): m.p.= 212°C, T_dec = 258°C

C/H/N Analysis calc.% (found): C 43.64 (43.77), H 5.86 (5.81), N 25.44 (24.24)

1H NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): 1.24 (t, 9H, CH₃), 3.14 (q, 6H, NCH₂), 6.65 (br, 1H, NH)

¹³C NMR (25 °C, CD₃CN, 300.13 MHz, delta in ppm): 9.29 (s, 3C, CH₃), 48.17 (s, 3C,

NCH₂)

¹⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -6.10 (d, 2F, ^ ^P) = 730 Hz, 2J(¹⁹F-¹³C) = 38 Hz, ²J(¹⁹F-¹³C) = 65 Hz) ³¹P NMR (25°C, CD₃CN, 300.13 MHz, delta in pm): -269.16 (t, IP, ^P-^F) = 730 Hz,

^P-^C) = 142 Hz, ^P-^C) = 218 Hz)

IR (25°C, ATR, 32 scans, v in cm^"1): 3116 (w), 2993 (w), 2952 (w), 2884 (w), 2822 (w),

2746 (w), 2203 (w), 2196 (w), 1660 (w), 1475 (m), 1464 (w), 1430 (w), 1395 (w), 1361 (w), 1290 (w), 1174 (w), 1158 (w), 1059 (w), 1029 (w), 1014 (w), 897 (w), 836 (w), 777

(s), 667 (s), 571 (m), 542 (m)

Example 10: Synthesis of compound of formula (7)

Example 8 was repeated with the difference that compound of formula (3) (0.208 g, 0.98 mmol), prepared according to example 5, and l-butyl-3-methylpyridinium bromide (0.226 g, 0.98 mmol) were used. Compound of formula (7) was obtained as a light yellow liquid (0.311 g, 98 %, 0.96 mmol). The liquid showed low viscosity.

DSC (10 K/min): T_gi_as = -93°C, T_dec = 272°C

C/H/N Analysis calc.% (found): C 52.01 (51.96), H 4.99 (4.99), N 21.66 (21.35)

1H NMR (25°C, D6-DMSO, 300.13 MHz, delta in ppm): 0.92 (t, 3H, CH₃-CH₂), 1.30 (sxt, 2H, CH₃-CH₂), 1.90 (quin, 2H, NCH₂-CH₂), 2.50 (s, 3H, CH₃-C), 4.54 (t, 2H, NCH₂), 8.03 (t, 1H, NCH-CH), 8.41 (d, 1H, NCH-CH-CH), 8.90 (d, 1H, NCH-CH), 8.98 (s, 1H, NCH-C)

1³C NMR (25 °C, CD₃CN, 300.13 MHz, delta in ppm): 14.26 (s, 1C, CH₃), 19.15 (s, 1C,

CH₃-CH₂), 20.52 (s, 1C, CH₃-C), 34.31 (s, 1C, NCH₂-CH₂), 63.09 (s, 1C, NCH₂), 127.68 (dt, 2C, CN, ^(^C-^P) = 218 Hz, ²J(¹³C-¹⁹F) = 65 Hz), 129.20 (s, 1C CH₃-C), 130.26 (dt, 2C, CN, ^C-^P) =143 Hz, ²J(¹³C-¹⁹F) = 38 Hz), 141.57 (s, 1C, NCH-CH), 143.11 (t, 1C, NCH-CH), 145.50 (t, 1C, NCH-C), 147.65 (s, 1C, NCH-CH-CH)

1⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -6.06 (d, 2F, ^(^F-^P) = 730 Hz, 2J(¹⁹F-¹³C) = 38 Hz, ²J(¹⁹F-¹³C) = 65 Hz)

3¹P NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -269.13 (t, IP, ^!J(³¹P-¹⁹F) = 730 Hz,

^P-^C) = 144 Hz, ^!J(³¹P-¹³C) = 216 Hz)

IR (25°C, ATR, 32 scans, v in cm^"1): 3074 (w), 2966 (w), 2938 (w), 2878 (w), 2201 (m), 2194 (m), 1678 (w), 1634 (w), 1595 (w), 1505 (m), 1482 (w), 1467 (w), 1386 (w), 1323

(w), 1253 (w), 1202 (w), 1158 (w), 1117 (w), 1097 (w), 1051 (w), 952 (w), 920 (w), 901 (w), 794 (s), 776 (s), 766 (s), 666 (s), 567 (m), 542 (m)

Example 11: Synthesis of compound of formula (8) Example 8 was repeated with the difference that compound of formula (3) (0.203 g, 0.96 mmol), prepared according to example 5, and 1 -butyl- 1-methylpyrrolidinium bromide (0.216 g, 0.97 mmol) were used. A colourless liquid of compound of formula (8) was obtained (0.296 g, 98 %, 0.94 mmol). The liquid showed low viscosity.

DSC (10 K/min): m.p.= -20°C, T_dec = 313°C

C/H/N Analysis calc.% (found): C 49.52 (49.34), H 6.39 (6.29), N 22.21 (21.53)

1H NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): 1.00 (t, 3H, CH₃-CH₂), 1.41 (sxt, 2H,

CH₃-CH₂), 1.75 (m, 2H, NCH₂-CH₂), 2.18 (m, 4H, NCH₂-CH₂), 2.96 (s, 3H, NCH₃), 3.24 (m, 2H, NCH₂), 3.42 (m, 4H, NCH₂)

¹³C NMR (25 °C, CD₃CN, 300.13 MHz, delta in ppm): 13.76 (s, 1C, CH₃), 20.36 (s, 1C,

CH₃-CH₂), 22.31 (s, 2C, NCH₂-CH₂), 26.22 (s, 1C, NCH₂-CH₂), 49.25 (t, 1C, NCH₃),

65.04 (t, 1C, NCH₂), 65.33 (t, 2C, NCH₂), 127.22 (dt, 2C, CN, ^(^C-^P) = 218 Hz,

²J(¹³C-¹⁹F) = 66 Hz), 128.13 (dt, 2C, CN, ^(^C-^P) = 143 Hz, ²J(¹³C-¹⁹F) = 38 Hz) ¹⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -6.08 (d, 2F, ^ ^P) = 730 Hz,

²J(¹⁹F-¹³C) = 38 Hz, ²J(¹⁹F-¹³C) = 66 Hz)

3¹P NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -269.16 (t, IP, ^P-^F) = 730 Hz,

^P-^C) = 143 Hz, ^!J(³¹P-¹³C) = 217 Hz).

IR (25°C, ATR, 32 scans, v in cm^"1): 2968 (w), 2939 (w), 2879 (w), 2201 (m), 2194 (m), 1675 (w), 1464 (m), 1430 (w), 1404 (w), 1385 (w), 1349 (w), 1304 (w), 1261 (w), 1121

(w), 1061 (w), 1030 (w), 1003 (w), 964 (w), 928 (w), 891 (w), 794 (s), 777 (s), 765 (s),

668 (s), 570 (m), 542 (m)

Example 12: Synthesis of compound of formula (9)

Example 8 was repeated with the difference that compound of formula (3) (0.218 g, 1.03 mmol), prepared according to example 5, and 1 -butyl- 1-methylpiperidinium bromide (0.243 g, 1.03 mmol) were used. Compound of formula (9) was obtained as a colourless liquid (0.297 g, 87 %, 0.90 mmol). The liquid showed low viscosity. DSC (10 K/min): m.p.= -29°C, T_dec = 299°C

C/H/N Analysis calc.% (found): C 51.06 (51.01), H 6.73 (6.66), N 21.27 (21.01)

1H NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): 1.01 (t, 3H, CH₃), 1.41 (sxt, 2H, CH₃-

CH₂), 1.69 (m, 4H, NCH₂-CH₂, NCH₂-CH₂-CH₂), 1.87 (m, 4H, NCH₂-CH₂), 2.96 (s, 3H,

NCH₃), 3.27 (m, 6H, NCH₂) ¹³C NMR (25 °C, CD₃CN, 300.13 MHz, delta in ppm): 13.79 (s, 1C, CH₃), 20.30 (s, 1C, CH₃-CH₂), 20.48 (s, 2C, NCH₂-CH₂), 21.56 (s, 1C, NCH₂-CH₂-CH₂), 24.23 (s, 1C, NCH₂-CH₂), 48.70 (s, 1C, NCH₃), 62.04 (s, 2C, NCH₂), 64.29 (s, 1C, NCH₂), 127.09 (dt, 2C, CN, ^(^C-^P) = 218 Hz, ²J(¹³C-¹⁹F) = 66 Hz), 129.67 (dt, 2C, CN, ^(^C-^P) = 143 Hz, ²J(¹³C-¹⁹F) = 38 Hz)

¹⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -6.05 (d, 2F, ^ ^P) = 731 Hz, 2J(¹⁹F-³¹P) = 38 Hz, ²J(¹⁹F-¹³C) = 66 Hz)

³¹P NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -269.06 (t, IP, ²J(³¹P-¹⁹F) = 731 Hz, ^P-^C) = 144 Hz, ^!J(³¹P-¹³C) = 217 Hz)

IR (25°C, ATR, 32 scans, v in cm^"1): 2966 (w), 2879 (w), 2201 (w), 2194 (w), 1678 (w),

1480 (w), 1464 (w), 1385 (w), 1365 (w), 1348 (w), 1320 (w), 1297 (w), 1273 (w), 1225 (w), 1184 (w), 1114 (w), 1083 (w), 1058 (w), 1028 (w), 993 (w), 972 (w), 937 (w), 901 (w), 884 (w), 863 (w), 794 (s), 777 (s), 765 (s), 668 (s), 595 (w), 569 (m), 542 (m) Example 13: Synthesis of compound of formula (10)

Example 8 was repeated with the difference that compound of formula (3) (0.316 g, 1.49 mmol), prepared according to example 5, and 1-ethylimidazolium bromide (0.264 g, 1.49 mmol) were used. Compound of formula (10) was obtained as a white solid (0.201 g, 50 %, 0.74 mmol).

C/H/N Analysis calc.% (found): C 40.01 (39.84), H 3.36 (3.49), N 31.11 (30.88)

1H NMR (25°C, CD₂C1₂, 300 MHz, delta in ppm): 1.60 (t, 3H, CH₃), 4.28 (q, 2H, CH₂), 7.36

(m, 1H, HN-CH), 7.40 (m, 1H, EtN-CH), 8.44 (s, 1H, NCHN), 11.65 (s, 1H, NH)

1³C NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): 15.63 (s, 1C, CH₃), 45.74 (s, 1C, CH₂), 121.17 (s, 1C, HN-CH), 122.65 (s, 1C, EtN-CH), 127.16 (dt, 2C, CN, ^(^C-^F)

218 Hz, ²J(¹³C-¹⁹F) = 66 Hz), 129.74 (dt, 2C, CN, ^!J(¹³C-³¹P) = 143 Hz, ²J(¹³C-¹⁹F) = 38

Hz), 135.40 (s, 1C, NCHN)

1⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -6.09 (d, 2F, ^!J(¹⁹F-³¹P) = 732 Hz,

²J(¹⁹F-¹³C) = 38 Hz, ²J(¹⁹F-¹³C) = 66 Hz)

3¹P NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -263.70 (t, IP, ^!J(³¹P-¹⁹F) = 731 Hz,

^!J(³¹P-¹³C) = 144 Hz, ^!J(³¹P-¹³C) = 220 Hz)

IR (25°C, ATR, 32 scans, v in cm^"1): 3159 (m), 3115 (m), 2991 (w), 2885 (w), 2202 (m),

2197 (m), 1639 (w), 1578 (m), 1549 (m), 1468 (w), 1448 (w), 1408 (w), 1390 (w), 1307 (w), 1394 (m), 1242 (w), 1153 (w), 1107(w), 1084 (m), 1018 (w), 966 (w), 777 (s), 665 (s), 619 (s), 571 (s), 542 (s)

Example 14: Synthesis of compound of formula (11)

Example 8 was repeated with the difference that compound of formula (3) (0.216 g, 1.02 mmol), prepared according to example 5, and l-butyl-2,3-dimethylimidazolium bromide (0.238 g, 1.02 mmol) were used. Compound of formula (11) was obtained as a light yellow liquid (0.316 g, 95 %, 0.97 mmol). The liquid showed low viscosity. DSC (2 K/min): m.p.= -3°C, T_dec = 282°C

C/H/N Analysis calc.% (found): C 47.85 (47.90), H 5.25 (5.28), N 25.76 (25.32)

1H NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): 0.95 (t, 3H, CH₃-CH₂), 1.36 (sxt, 2H, CH₃-CH₂), 1.75 (quin, 2H, NCH₂-CH₂), 2.50 (s, 3H, CH₃-C), 3.70 (s, 3H, NCH₃), 4.03 (t, 2H, NCH₂), 7.23 (d, 1H, CH₂-NCH), 7.25 (d, 1H, CHN-CH₃)

1³C NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): 10.04 (s, 1C, CH₃-CH₂), 13.73 (s, 1C, CH₃-C), 20.08 (s, 1C, CH₃-CH₂), 32.21 (s, 1C, NCH₂-CH₂), 35.71 (s, 1C, NCH₃), 48.98 (s, 1C, NCH₂), 121,74 (s, 1C, CH₂-NCH₂), 123.20 (s, 1C, CH₂-NCH₃), 127.07 (dt, 2C, ^(^C-^P) = 218 Hz, ²J(¹³C-¹⁹F) = 66 Hz), 129.67 (dt, 2C, ^(^C-^P) = 143 Hz, ²J(¹³C- 1⁹F) = 38 Hz), 145.29 (s, 1C, CH₃-C)

1⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -6.07 (d, 2F, ^ ^P) = 730 Hz, 2J(¹⁹F-¹³C) = 38 Hz, ²J(¹⁹F-¹³C) = 66 Hz)

3¹P NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -262.54 (t, IP, ^P-^F) = 730 Hz,

^P-^C) = 144 Hz, ^!J(³¹P-¹³C) = 218 Hz).

IR (25°C, ATR, 32 scans, v in cm^"1): 3186 (w), 3152 (w), 2965 (w), 2938 (w), 2878 (w), 2201 (m), 2194 (m), 1678 (w), 1590 (w), 1538 (w), 1517 (w), 1464 (w), 1421 (w), 1385

(w), 1342 (w), 1300 (w), 1269 (w), 1249 (w), 1239 (w), 1183 (w), 1136 (w), 1106 (w), 1077 (w), 1039 (w), 948 (w), 795 (s), 777 (s), 741 (s), 666 (s), 570 (m), 542 (m)

Example 15a

[(n-Bu)4N][PF₆] (410 mg, 1.06 mmol), prepared according to Preparation Description (1), and (CH₃)₃SiCN (1.05 g, 10.6 mmol) were stirred under argon atmosphere at ambient temperatures for three hours. A sample of the obtained reaction mixture was analyzed by ¹⁹F NMR: the reaction mixture contained a mixture of about 87 % of compound of formula (13) and 13 % of compound of formula (14). ¹⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -77.56 (dquin, IF, PF₅(CN)_, ^P-^F) = 758 Hz, ²J(¹⁹F-¹⁹F) = 54 Hz), -54.31 (dt, 2F, cis-PF₄(CN₂), ^P-^F) = 765 Hz, ²J(¹⁹F- 1⁹F) = 43 Hz), -48.85 (dd, 4F, PF₅(CN)_, ^P-^F) = 739 Hz, ²J(¹⁹F-¹⁹F) = 54 Hz), -41.26 (dt, 2F, cis-PF₄(CN₂), ^P-^F) = 713 Hz, ²J(¹⁹F-¹⁹F) = 42 Hz)

Example 15b

A reaction mixture prepared according to example 15a was refluxed for eight hours. After cooling to ambient temperatures a sample of the resulting reaction was analyzed by ¹⁹F NMR: the reaction mixture contained a mixture of about less than 1 % of compound of formula (13), 95 % of compound of formula (14a) and 4 % of compound of formula (15). Compound of formula (14a) is a mixture of 52 % (14b) and 48 % (14).

¹⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -54.31 (dt, 2F, cis-PF₄(CN₂), ^!J(³¹P- 1⁹F) = 765 Hz, ²J(¹⁹F-¹⁹F) = 43 Hz), -48.85 (dd, 4F, PF₅(CN)_, ^P-^F) = 739 Hz, ²J(¹⁹F- 1⁹F) = 54 Hz), -41.26 (dt, 2F, cis-PF₄(CN₂)_, ^P-^F) = 713 Hz, ²J(¹⁹F-¹⁹F) = 42 Hz), - 40.05 (dd, IF, mer-PF₃(CN)₃, ¹ J(³¹P-¹⁹F) = 680 Hz, ²J(¹⁹F-¹⁹F) = 33 Hz), -31.48 (d, 4F, trans-PF₄(CN₂)_, ^P-^F) = 739 Hz), -9.91 (dt, 2F, mer-PF₃(CN)₃, ^P-^F) = 777 Hz, 2J(¹⁹F-¹⁹F) = 35 Hz)

Example 16

[(n-Bu)₄N][PF₆] (320 mg, 0.84 mmol), prepared according to Preparation Description (1), and (CH₃)₃SiCN (819 mg, 8.36 mmol) were filled under argon atmosphere with a residual oxygen content of

below 5 ppm and with a residual water content of below 1 ppm into a teflon tube of an autoclave. The autoclave was placed inside a muffle furnace and heated to 150°C within 30 minutes. The temperature was held for 15 h.

After cooling to ambient temperature a sample of the obtained reaction mixture was analyzed by ¹⁹F NMR: the reaction mixture contained a mixture of about less than 1 % of compound of formula (14b), 93 % of compound of formula (15a) and 6 % of compound of formula (la). Compound of formula 15a is a mixture of 60 % (15) and 40 % (15b). Compound of formula (la) is a mixture of 91 % (1) and 9 % (lb).

¹⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -48.70 (d, 2F, trans-PF₂(CN)₄, ^!J(³¹P- 1⁹F) = 633 Hz), -41.58 (d, 3F, fac-PF₃(CN₃), ^P-^F) = 740 Hz), -40.02 (dd, IF, mer-

PF₃(CN)₃, ^P-^F) = 687 Hz, ²J(¹⁹F-¹⁹F) = 33 Hz), -31.43 (d, 4F, trans-PF₄(CN₂), ^P-^F) = 740 Hz), -9.86 (dt, 2F, mer-PF₃(CN)₃, ^P-^F) = 777 Hz, ²J(¹⁹F-¹⁹F) = 35 Hz), -6.05 (d, 2F, cis-PF₂(CN)₄, ^P-^F) = 730 Hz) Example 17

Example 16 was repeated with the differences:

1. [(n-Bu)₄N][PF₆] (447 mg, 1.15 mmol) and (CH₃)₃SiCN (2.29 g, 23.1 mmol) were used.

2. The temperature was 200°C instead of 150°C, which was held for 13 h instead of 15 h. After cooling to ambient temperature a sample of the obtained reaction mixture was analyzed by ¹⁹F and ³¹P NMR: the reaction mixture contained a mixture of about 90 % of compound of formula (1) and 10 % of compound of formula (21).

¹⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -6.05 (d, 2F, cis-PF₂(CN)₄, ^P-^F) = 730 Hz), 20.1 (d, IF, PF(CN)₅, ^P-^F) = 708 Hz)

3¹P NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -268.6 (t, 2F, cis-PF₂(CN)₄, ^P-^F) = 730 Hz), -316.5 (d, IF, PF(CN)₅, ^P-^F) = 708 Hz)

Example 18

A solution of [(n-Bu)₄N]Cl (402 mg, 1.44 mmol) in (CH₃)₃SiCN (2.77 g, 28 mmol) was added via a syringe in ca. 10 min to a solution of PCI₅ (300 mg, 1.44 mmol) in 5 ml CH₂C1₂, the CH₂C1₂ was dried over CaH₂ prior to its use. After three hours of stirring at ambient temperature a sample of the obtained reaction mixture was analyzed with ³¹P NMR: the reaction mixture contained a mixture of about 78 % of [(n-Bu)₄N][PCl(CN)₃], 15 % of compound of formula (17) and 7 % of compound of formula (18). Compound of formula (18) is a mixture of 90 % of compound of formula (18b) and 10 % of compound of formula (18a).

P NMR (25°C, CD₂C1₂, 300.13 MHz, delta in ppm): -355.2 (s, IP, trans-PCl₂(CN)₄), -351.3 (s, IP, fac-PCl₃(CN)₃), -338.8 (s, IP, mer-PCl₃(CN)₃), -189.14 (s, IP, PC1(CN)₃) Example 19

A solution of PC1₅ (306 mg, 1.47 mmol) in 5 ml CH₂C1_2, the CH₂C1₂ was dried over CaH₂ prior to its use, was slowly added via a syringe in ca. 10 min to a solution of [(n-Bu)₄N]Cl (408 mg, 1.48 mmol) in (CH3)3SiCN (2.37 ml, 24 mmol). The resulting mixture was stirred for three hours of stirring at ambient temperature, then a sample of the obtained reaction mixture was analyzed with ³¹P NMR: the reaction mixture contained about less than 1% of compound of formula (18), 18 % of compound of formula (19) and 81 % of compound of formula (20). ^J1P NMR (25°C, CD₂C1₂, 300.13 MHz, delta in ppm): -330.5 (s, IP, cis-PCl₄(CN)₂), -314.8 (s, IP, trans-PCl₄(CN)₂)

Example 20: Synthesis of compound of formula (22)

20 ml of the acidic ion exchanger Dowex HCR-W2 were filled into a column. The ion exchanger was treated with aqueous hydrochloric acid (5 wt%) prior to use. Afterwards the acidic ion exchanger was washed with water until the common AgN0₃ test for chloride ions was negative. 1 g (4.7 mmol) of compound of formula (3), prepared according to example 5, was dissolved in 10 ml of deionized water and transfered onto the top of the column. The solution was allowed to pass through the ion exchanger column. The product was washed with water until the pH value of the eluate was around 6. The eluate was concentrated on a rotary evaporator. After drying the resulting white solid in vacuo at 70°C 0.84 g (4.37 mmol, 93 %) of compound of formula (22) were obtained.

C/H/N Analysis calc.% (found): C 25.01 (24.36), H 1.57 (1.73), N 29.17 (27.38)

1H-NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): 8.9 (br)

¹⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -6.10 (d, 2F, ^(^F-^P) = 730 Hz,

²J(¹⁹F-¹³C) = 37 Hz, ²J(¹⁹F-¹³C) = 65 Hz)

3¹P NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -269.19 (t, IP, ^P-^F) = 730 Hz, ^P-^C) = 143 Hz, ^P-^C) = 215 Hz)

IR (25°C, ATR, 32 scans, v in cm^"1): 3107 (m), 2229 (w), 2218 (w), 1723 (m), 1033 (m), 794 (s), 645 (s), 564 (s), 536 (s)

In order to obtain crystals suitable for x-ray crystal structure determination an aqueous solution of compound of formula (22) prepared as described was slowly evaporated in an exsiccator. Colorless crystals were formed and were suitable for x-ray crystal structure determination. The x-ray crystal structure determination revealed the elemental formula

[H₅02][cis-PF₂(CN)4] , compound of formula (25). Example 21: Synthesis of compound of formula (23)

To an aqueous MgCl₂ solution (1 g MgCl₂ in 10 ml H₂0) aqueous NH₃ solution (0.5 ml, 25 wt%) was added. The resulting suspension of Mg(OH)₂ was filtered and washed 3 times with water. Thus prepared Mg(OH)₂ was added to 10 ml of an aqueous solution of

[H₃0][PF₂(CN)4] (0.111 g, 0.58 mmol, prepared according to example 20) until the pH reached the value 7. The resulting suspension was filtered. The filtrate was concentrated on a rotary evaporator. After drying the resulting white solid in vacuo at 60 °C 0.12 g (0.27 mmol, 94 %) of compound of formula (23) were obtained.

TGA/DSC (5 K/min): 101 °C loss of two equivalents of water, 212 °C loss of two equivalents of water, 267 °C start of decomposition

C/H/N Analysis calc.% (found): C 21.72 (21.56), H 1.82 (1.54), N 25.33 (24.12)

¹⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -6.11 (d, 2F)

³¹P NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -269.15 (t, IP)

IR (25°C, ATR, 32 scans, v in cm^"1): 3373 (m), 2212 (w), 2162 (w), 1629 (m), 800 (s), 668 (s), 567 (s), 537 (s)

Example 22: Synthesis of compound of formula (24)

Example 21 was repeated with the difference that [H₃0][PF₂(CN)4] (0.17 g, 0.89 mmol), prepared according to example 20, were used, and ZnO (0.16 g, 2 mmol) instead of Mg(OH)₂ were used. Compound of formula (24) was obtained as a white solid (0.19 g, 95 %, 0.42 mmol).

TGA/DSC (5 K min): 150 °C loss of one equivalent of water, 174 °C loss of one equivalent of water, 202 °C start of decomposition

C/H/N Analysis calc.% (found): C 21.47 (21.05), H 0.90 (0.74), N 25.04 (23.52)

1⁹F NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -6.10 (d, 2F)

3¹P NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): -269.70 (t, IP)

IR (25°C, ATR, 32 scans, v in cm^"1): 3416 (m), 2343 (w), 2212 (w), 2139 (w), 1632 (w), 808 (m), 652 (m), 573 (m), 542 (m) RAMAN (25°C, 12 mW, 4 scans, cm^"1): 2309 (s), 2249 (s), 2241 (s), 2215 (w), 2206 (s), 2197 (s), 2115 (s), 1103 (w), 1036 (w), 855 (w), 805 (w), 571 (m), 522 (m), 516 (m), 490 (w), 472 (w), 408 (w), 394 (w), 371 (m), 248 (w), 239 (w), 231 (w), 197 (w), 174 (m)

In order to obtain crystals suitable for x-ray crystal structure determination, a small amount of the powder was dissolved in a small amount of acetonitrile and the solvent was evaporated by letting the solution stand in an open flask over night. The crystals formed were suitable for x- ray crystal structure determination. The x-ray crystal structure determination confirmed the structure.

Application example and comparison with EMIm[PF₃(CN)3]

Compound was tested in dye sensitized solar cells.

DMII 1 ,3 -dimethylimidazolium iodide

EMU l-ethyl-3-methylimidazo Hum iodide

EMI 1 -ethyl-3 -methylimidazolium

NBB n-butylbenzimidazol

GITC guanidinium thiocyanate The individual compound tested is called compound TEST in the following. Compound TEST was

1. Compound of formula (5), which was prepared according to example 7.

2. Comparative Compound: EMIm[PF3(CN)3] , which is available according to example 4 of EP 2 410 601 Al .

Device fabrication: Photo anodes used to make the devices consisted of a screen-printed nanoparticulate mesoporous Ti0₂ layers. A 8 μιη thick transparent layer of 20 nm sized Ti0₂ particles was first printed on the fluorine doped Sn0₂ (FTO) conducting glass (purchased from NSG with 10 Ω/cm², 4 mm thick) and subsequently coated with a 5 μιη thick second layer of 400 nm light-scattering anatase particles (CCIC, Japan). Detailed procedures for the preparation of Ti0₂ nanoparticles and pastes are reported in Ito, S. et al, Prog. Photovolt. Res. AppL, 2007, 15, 603. A standard C106 dye with CAS 1165943-93-0 was used as the sensitizer with the addition of dineohexyl bis-(3,3-dimethyl-butyl)-phosphinic acid

(DINHOP) as a co-adsorbent (4: 1 ratio) in a solvent mixture of 10% DMSO and tert-butanol and acetonitrile (1 : 1) v/v ratio. The above-described double-layered Ti0₂ films were sintered for 30 min at 500° C and immersed in the dye solution for 16 h. After sensitization they were rinsed in pure MeCN and assembled with platinized counter electrodes. The counter electrodes were prepared using conducting glass TEC 15 (purchased from NSG, resistance 15 Ω/cm², 2 mm thick) on which the drop of a solution of hexachloroplatinate acid in n-propanol was cast. Thermal platinization occurred during heating the electrodes twice for 15 min at 425 °C in air. Electrodes were then sealed with a 25 micrometer thick hot-melt film (Surlyn®, Dupont) by heating the system at 100°C.

The composition of the electrolyte B, which was used, is:

electrolyte A = DMII/EMII/compound TEST /I₂/NBB/GITC (12/12/16/1.67/3.33/0.67) electrolyte B = electrolyte A + sulfolane (50:50 v/v).

Devices were completed by filling the space between the electrodes with electrolyte through pre-drilled holes in the counter electrodes and the holes were sealed with a Surlyn sheet and a thin glass cover by heating. Finally, metal contacts were placed on both electrodes.

Photovoltaic measurements: Photovoltaic measurements were performed under simulated sun irradiance (100 mW cm^"2, equivalent of 1 sun at air mass global, AM 1.5 G, at the surface of the device) provided by a 450 W Xenon light source (Oriel, USA). A Schott Kl 13 Tempax sunlight filter (Prazisions Glas & Optik GmbH, Germany) was used to correct the spectral output of the lamp in the region 350 to 750 nm. Current to voltage characteristics (in the dark and under illumination) were obtained by applying a forward potential bias and measuring resulting current with a Keithley 2400 digital sourcemeter (Keithley, USA). A metal mask was used to precisely define the irradiated surface area (0.159 cm²). Quantum efficiencies of the cells were measured by using a SR830 lock in amplifier, however the incident light (300 W xenon lamp, ILC Technology) was focused through a Gemini- 180 double monochromator (Jobin-Yvon Ltd.). The cells were measured with an external light bias (100% Sun) provided by LED array. A black metal mask defined the cell active area to be 0.159 cm².

Results

The photovoltaic parameters of devices containing electrolyte B @ 60 °C using Pt as a counter electrode are shown in table 1 at 1 sunlight.

The tables show the photovoltaic parameters of CI 06 dye based devices measured under irradiation of 100 mW cm^"2 AM 1.5 G Sunlight.

The higher the efficiency the better. Abbreviations of Table 1 :

J_sc short circuit photo current

V_oc open circuit voltage

FF fill factor

η efficiency

nd not determined

The efficiency of compound of formula (5) is high than the efficiency of EMIm[PF₃(CN)3] . Electrochemical Window

Pt wires were cleaned thoroughly before each measurement. The compound TEST was placed in a glass flask and purged with dry Argon for 30 min. The Pt wires served as a working electrode, as counter electrode and as pseudo reference electrode. After the cyclovoltagrams ferrocene (Fc) was added to normalize the voltage scale to this outer sphere redox couple. The larger the electrochemical window the better.

Resultsa are shown in Table 2.

Table 2

Compound TEST Electrochemical Window

[ V ]

compound of formula (5) 4,3

EMIm[PF₃(CN)₃] 4,1 The electrochemical window of compound of formula (5) is larger than the one of

EMIm[PF₃(CN)₃].

Further comparison of compounds

Comparison 1:

Comparison of compound of formula (5) against EMIm[PF₃(CN)₃] with respect to stability against acids 100 mg of compound of formula (5), prepared according to example 7, were mixed with 100 mg of a 2 molar aqueous solution of hydrochlorid acid. The mixture was heated to 50 °C and the temperature was held for 24 hours. A sample of the obtained reaction mixture was analyzed with the aid of ³¹P NMR. The NMR spectra showed no difference or byproducts with respect to the ³¹P NMR spectra of compound of formula (5) before mixing with hydrochloric acid.

The same procedure was carried out with EMIm[PF₃(CN)₃], which is available according to example 4 of EP 2 410 601 Al . The ³¹P NMR spectra showed two new signals, one at 0 ppm and one at 4 ppm.

This shows that compound of formula (5) is more stable against hydrochloric acid than EMIm[PF₃(CN)₃].

Comparison 2:

Comparison of the melting points of compound of formula (5) and EMIm[PF₃(CN)₃]

The melting points were determined with the aid of DSC measurements with a heating rate of 10 K per min. The melting point of compound of formula (5), prepared according to example 7, is -32 °C, that is 16 °C below the melting point of EMIm[PF₃(CN)₃], which is available according to example 4 of EP 2 410 601 Al, with -16 °C. This shows that compound of formula (5) has a wider range of application at low temperatures.

Comparison 3:

Comparison between compound of formula (4) and Li[PF₃(CN)₃] with respect to thermal stability The decomposition temperatures were determined with the aid of TGA/DSC measurements using a heating rate of 5 K per min. Compound of formula (4), prepared according to example 6 starts to decompose at 267 °C and is more stable than Li[PF₃(CN)₃], which is available according to EP 2 587 580 Al Example 1, which starts to decompose at 250°C. This shows that compound of formula (4) has a wider range of applications.

Claims

1. Compound of formula (I), wherein

compound of formula (I) is selected from the group consisting of compound of formula (lb), compound of formula (Ic), compound of formula (Id), compound of formula (le), compound of formula (If) and compound of formula (Ig);

[Catⁿ⁺] [(PFi(CN)₅)^" ]_n (lb)

[Catⁿ⁺] [(PF₄(CN)₂)^" ]„ (Ic)

[Catⁿ⁺] [(PF₅(CN))^" ]„ (Id)

[Catⁿ⁺] [(PC1₂(CN)₄)^" ]„ (le)

[Catⁿ⁺] [(PC1₃(CN)₃)^" ]_n (if)

[Catⁿ⁺] [(PC1₄(CN)₂)^" ]_n (ig)

cation CatORG ;

n is 1, 2, 3 or 4;

CatINORGⁿ⁺ is a cation selected from the 1.,

2.,

3.,

4.,

5.,

6.,

7.,

8.,

9.,

10.,

11.,

12.,

13.,

14.,

CatORG is selected from the group consisting of CatORG- A , CatORG-B , CatORG- C⁺, CatORG-D⁺, CatORG-E⁺, guanidinium and (H₂(R18)N-R16-N(R19)H₂)²⁺;

CatORG-A is (WR2R3R4R5) ,

wherein

W is a nitrogen or phosphorus; and

(i) R2, R3, R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_₂₀ alkyl, Ci_₂₀ perfluoroalkyl, C3-10 cycloalkyl and C₆-io aryl, with the proviso, that at least one of the residues R2, R3, R4 and R5 is not H; or

7-membered saturated or unsaturated heterocyclic ring,

R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_₂o alkyl, Ci_₂o perfluoroalkyl, C3-10 cycloalkyl and C₆_io aryl; or

CatORG-B⁺ is (XR6R7R8)⁺,

wherein

X is nitrogen,

perfluoroalkyl, C3-10 cycloalkyl or C₆-io aryl;

CatORG-C⁺ is (YR9R10R11)⁺,

wherein

Y is sulphur;

perfluoroalkyl, C3-10 cycloalkyl and C₆-io aryl; or

7-membered saturated or unsaturated ring,

Rl 1 is selected from the group consisting of H, Ci_₂₀ alkyl, Ci_₂₀ perfluoroalkyl, C3-10 cycloalkyl and C₆-io aryl;

CatORG-D⁺ is (ZR12R13)⁺,

wherein Z is oxygen or sulphur;

R12 and R13 together are a hydrocarbon chain and form together with Z a 5- to 7-membered heterocyclic ring in which Z is connected by a single bond and a double bond to R12 and R13 respectively;

CatORG-E⁺ is a cyclic C_nx alkane or a cyclic C_nx alkene bearing a positive charge, wherein

nx is 3, 5, 7 or 9,

said cyclic C_nx alkene has 1 double bond in case of nx being 3, 2 double bonds in case of nx being 5, 3 double bonds in case of nx being 7, and 4 double bonds in case of nx being

9,

with R14 and R15 are identical or different and independently from each other selected from the group consisting of H and Ci_₆ alkyl; the residues R2, R3, R4, R5, R6, R7, R8, R9, RIO, Rl 1 , R12 and R13 are, independently from each other, unsubstituted or, where applicable, substituted by 1 , 2, 3, 4, 5 or 6 substituents selected from the group consisting of Ci_₄ alkyl, C₃_io cycloalkyl, C₂_s alkenyl, phenyl, benzyl, halogen, cyano and Ci_₄ alkoxy; any of said hydrocarbon chains formed by R2 and R3, by R4 and R5, by R6 and R7, by R9 and RIO, and by R12 and R13, 1 or 2 carbon atoms of said hydrocarbon chains can be exchanged for 1 or 2 heteroatoms respectively, said one or two heteroatoms being selected from the group consisting of O, N and S; in case of an exchange for N, this N is unsubstituted or substituted by a residue selected from the group consisting of Ci_s alkyl, C₃_io cycloalkyl, C₂_s alkenyl and Ci_s perfluoroalkyl; R16 is selected from the group consisting of C₂_₈ alkylen, C₃_₈ cycloalkylen, phenylen, C(H)(phenyl), R17(-0-R17)„i;

R17 is selected from the group consisting of CH₂-CH₂, CH₂-CH₂-CH₂, CH₂-C(H)(CH₃)- CH₂, CH₂-CH₂-C(H)(CH₃) and CH₂-CH₂-CH₂-CH₂; R18 and R19 are identical or different and independently from each other selected from the group consisting of H, Ci_₈ alkyl, C₃_₈ cycloalkyl, phenyl and benzyl;

nl is an integer from 1 to 20. 2. Compound of formula (I) according to claim 1 , wherein

CatINORGⁿ⁺ is a cation selected from the 1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 1 1., 12., 13., 14. or 15. group of the periodic table or is a cation from the lanthanides, NH₄ ⁺, H₃0⁺ or H5O2 .

3. Compound of formula (I) according to claim 1 or 2, wherein

CatINORGⁿ⁺ is a cation selected from the 1., 2., 4., 5., 6., 7., 8., 9., 10., 1 1., 12., 13., 14. or 15. group of the periodic table or is a cation from the lanthanides, NH₄ ⁺, H₃0⁺ or H5O2 .

4. Compound of formula (I) according to one or more of claims 1 to 3, wherein

CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ti⁴⁺, Ti³⁺, Zr⁴⁺, Zr³⁺, Hf⁴*, n ⁺, V⁴⁺, V³⁺, V²⁺, Nb⁴⁺, Ta⁴⁺, Cr³⁺, Mo⁴⁺,

Mo³⁺, Mo²⁺, W⁴⁺, W³⁺, W²⁺, Mn⁴⁺, Mn³⁺, Mn²⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Ru⁴⁺, Ru³⁺, Ru²⁺, Os⁴⁺, Os³⁺, Os²⁺, Co⁴⁺, Co³⁺, Co²⁺, Rh⁴⁺, Rh³⁺, Ir⁴⁺, Ir³⁺, Ni⁴⁺, Ni³⁺, Ni²⁺, Pd⁴⁺, Pd³⁺, Pd²⁺, Pt⁴⁺, Pt³⁺, Pt²⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, Ag⁴⁺, Ag³⁺, Ag²⁺, Ag⁺, Au³⁺, Au²⁺, Au⁺, Zn²⁺, Zn⁺, Cd²⁺, Cd⁺, Hg²⁺, Hg⁺, B³⁺, Al³⁺, Ga³⁺, Ga⁺, In³⁺, In⁺, Tl³⁺, Tl⁺, Ge⁴⁺,Ge²⁺, Sn⁴⁺,Sn²⁺, Pb⁴⁺, Pb²⁺, As³⁺, Sb³⁺, Bi³⁺, Bi¹⁺, La³⁺, Nb³⁺, Sm³⁺, Eu³⁺, Gd³⁺, NH₄ ⁺, H₃0⁺ and H₅0₂ ⁺.

5. Compound of formula (I) according to one or more of claims 1 to 4, wherein

CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Ti⁴⁺, Ti³⁺,

Zr⁴⁺, Zr³⁺, V⁴⁺, V³⁺, V²⁺, Cr³⁺, Mo⁴⁺, Mo³⁺, Mo²⁺, W⁴⁺, W³⁺, W²⁺, Mn⁴⁺, Mn³⁺, Mn²⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Ru⁴⁺, Ru³⁺, Ru²⁺, Co⁴⁺, Co³⁺, Co²⁺, Rh⁴⁺, Rh³⁺, Ir⁴⁺, Ir³⁺, Ni⁴⁺, Ni³⁺, Ni²⁺,

Pd⁴⁺, Pd³⁺, Pd²⁺, Pt⁴⁺, Pt³⁺, Pt²⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, Ag⁴⁺, Ag³⁺, Ag²⁺, Ag⁺, Zn²⁺, Zn⁺, Al³⁺, Ga³⁺, Ga⁺, In³⁺, In⁺, Sn⁴⁺,Sn²⁺, Pb⁴⁺, Pb²⁺, Sb³⁺, Nb³⁺, Sm³⁺, Eu³⁺, Gd³⁺, NH₄ ⁺, H₃0⁺ and H₅0₂ ⁺. 6. Compound of formula (I) according to one or more of claims 1 to 5, wherein CatlNORG" is selected from the group consisting of Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Ti⁴⁺, V⁴⁺,

V³⁺, V²⁺, Cr³⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Co⁴⁺, Co³⁺, Co²⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, A

Zn , Al³⁺, Sn⁴⁺,Sn²⁺, Pb⁴⁺, Pb²⁺, Sb³⁺, Eu ⁺, Gd³⁺, NH₄ ⁺, H₃0⁺ and H₅0₂ ⁺.

7. Compound of formula (I) according to one or more of claims 1 to 6, wherein n in CatORGⁿ⁺ is 1.

8. Compound of formula (I) according to one or more of claims 1 to 7, wherein

CatORG is selected from the group consisting

, [N(R20)(R21)(R22)R23]' and [P(R20)(R21)(R22)R23]⁺; wherein

R20 is Ci_2o alkyl or C₃_io cycloalkyl;

R21, R22 and R23 are identical or different and independently selected from the group consisting of H and Ci_₂o alkyl.

9. Compound of formula (I) according to one or more of claims 1 to 8 wherein

CatORG is selected from the roup consisting

[NH(C₄H₉)₃]⁺, [N(C₂H₅)₄]⁺, [N(C₄H₉)₄f, [P(C₂H₅)₄]^† and [P(C₄H₉)₄]

wherein

R20, R22 is Ci_-20 alkyl or C₃_i₀ cycloalkyl; R21 is H and C i_₂o alkyl.

10. Compound of formula (I) according to one or more of claims 1 to 7, wherein

Cat is a cation (Cat-Part 1); cation (Cat-Parti) is CatINORGⁿ⁺ or CatORGⁿ⁺,

tl-!- _l_ __|_ __|_ 2~_|- with CatlNORG selected from the group consisting of Li , Na , K , Mg , Ca , Zn

Ag⁺, H₃0⁺ and H₅0₂ ⁺, preferably of Li⁺, K⁺, Ag⁺, H₃0⁺ and H₅0₂ ⁺; and

with CatORG selected from the group consisting of

[NH(C₄H₉)₃]⁺, [N(C₂H₅)₄]⁺ and [N(C₄H₉)₄]⁺ and [P(C₄H₉)₄]⁺;

R20 is methyl, ethyl, propyl, butyl or cyclohexyl;

R21 is H, methyl or ethyl;

R22 is H or methyl. 1 1. Compound of formula (I) according to one or more of claims 1 to 7, wherein

CatORGⁿ⁺ is selected from the group consisting of cyclopropenylium, 1 ,2,3- triphenylcyclopropenylium, tri-tert-butylcyclopropenylium, 1 ,2,3- tris(diethylamino)cyclopropenylium, 1 ,2,3-tris(trimethylsilyl)cyclopropenylium and tropylium, 1 ,2,3, 4,5, 6,7-heptaphenylcyclohepta-2,4,6-trien-l-ylium.

12. Compound of formula (I) according to claim 1 , wherein

+ - 2+ compound of formula (I) is selected from the group consisting of Li [(PF(CN)₅) ], Mg

[(PF(CN)₅)^"]₂, Zn²⁺ [(PF(CN)₅)^"]₂, Ca²⁺ [(PF(CN)₅)^"]₂, [N(n-Bu)₄]⁺ [(PF(CN)₅)^"], [P(n-

Bu)₄]⁺ [(PF(CN)₅)^"],

13. Compound of formula (I) according to claim 1, wherein

compound of formula (I) is selected from the group consisting of compound of formula (13), compound of formula (14), compound of formula (14a), compound of formula (14b), compound of formula (15), compound of formula (15a), compound of formula (15b), compound of formula (17), compound of formula (18), compound of formula (18a), compound of formula (18b), compound of formula (19), compound of formula (20), compound of formula (21), and mixtures thereof.

[(n-Bu)₄N][PF₅(CN)] (13)

[(n-Bu)₄N][cis-PF₄(CN)₂] (14)

[(n-Bu)₄N] [PF₄(CN)₂] , mixture of cis and trans (14a)

[(n-Bu)₄N][trans-PF₄(CN)₂] (14b)

[(n-Bu)₄N][mer-PF₃(CN)₃] (15)

[(n-Bu)₄N][PF₃(CN)₃], mixture of fac and mer (15a)

[(n-Bu)₄N][fac-PF₃(CN)₃] (15b)

[(n-Bu)₄N][trans-PCl₂(CN)₄] (17)

[(n-Bu)₄N][PCl₃(CN)₃] ], mixture of fac and mer (18)

[(n-Bu)₄N][fac-PCl₃(CN)₃] (18a)

[(n-Bu)₄N][mer-PCl₃(CN)₃] (18b) [(n-Bu)₄N] [trans-PCl₄(CN)₂] (19)

[(n-Bu)₄N] [cis-PCl₄(CN)₂] (20) [(n-Bu)₄N][PF(CN)₅] (21)

14. Use of compound of formula (I), with compound of formula (I) as defined in any one of claims 1 to 13,

as solvent, as phase-transfer catalyst, as extractant, as heat-transfer medium, as surface-active substance, as plasticizer, as conductive salt, organic salt or additive in electrochemical cells, as electrolyte; as lubricant, as hydraulic fluid or as component in electrolyte formulations, in electrochemical and/or optoelectronic devices.

15. Use according to claim 14 of compound of formula (I) as component in electrolyte

formulations,

wherein said electrolyte formulations comprising a compound of formula (I) are used in electrochemical and/or optoelectronic devices;

wherein the electrochemical and/or optoelectronic devices are selected from the group

consisting of batteries, capacitors, supercapacitors, electrochemical cells, photovoltaic cell, light emitting device, electrochromic or photo-electrochromic device,

electrochemical sensor or biosensor, and dye sensitized solar cell.

16. Electrolyte formulation (ElFormul) which comprises compound of formula (I), with compound of formula (I) as defined in any one of claims 1 to 13.

17. Electrolyte formulation (ElFormul) according to claim 16, which comprises a solvent (ElSolv);

solvent (ElSolv) is selected from the group consisting of

ethylene carbonate, propylene carbonate, gamma-butyrolactone, gamma-valerolactone, delta- valerolactone, 1 ,2-dimethoxy ethane, diethoxy ethane, ethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, 1 ,4-dioxane, ethanol, ethylene glycol monomethyl ether, polyethylene glycol monoalkyl ether, ethylene glycol, propylene glycol, polyethylene glycol, tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile,

glutarodinitrile, propionitrile, valeronitrile, methoxyacetonitrile, benzonitrile, methyl acetate, ethyl acetate, ethyl propionate, trimethyl phosphate, triethyl phosphate, N- methylpyrrolidone, 2-methyl-l,3-dioxolane, N-butylbenzimidazole, sulfolane, dimethyl sulfoxide, formamide, Ν,Ν-dimethylformamide, nitromethane, and mixtures thereof.

18. Electrolyte formulation (ElFormul) according to claim 16 or 17, which comprises a salt (ElSalt), salt (ElSalt) is an iodide of a metal ion of the first main group of the periodic table.

19. Electrolyte formulation (ElFormul) according to one or more of claims 16 to 18, which comprises a compound (IonLiqu),

compound (IonLiqu) is compound of formula (I-Cat-n), with compound of formula (I-Cat-n) as defined in claim 1.

20. Electrolyte formulation (ElFormul) according to claim 19, wherein

compound (IonLiqu) is compound of formula (I-IonLiqu);

(CatORGⁿ )ti (AnINORG^q")t2 (I-IonLiqu)

AnINORG is an anion selected from the group consisting of Br , I , SCN , BF₄ , PF₆ , CF₃SO₃ , (CF₃S0₂)₂N , (FS0₂)₂N , anions of Ci_₂o monocarboxylic aliphatic acids, N(CN)₂ ^", C(CN)₃ ^", B(CN)₄ ^", and mixtures thereof; and

+

CatORGⁿ⁺ is selected from the group consisting of ^{CH;? n"C}4^H , 1 .

dimethylimidazolium, 1 -ethyl-3-methylimidazolium, 1 -propyl-3-methylimidazolium, 1 -allyl-3 -methylimidazolium, 1 -methyl-3 -hexylimidazolium, 1 -ethylimidazolium, l-butyl-2,3-dimethylimidazolium and mixture thereof;

n is 1;

q is 1;

tl is 1;

t2 is 1.

21. Electrolyte formulation (ElFormul) according to claim 19, wherein

compound (IonLiqu) is compound of formula (II-IonLiqu);

(CatINORGⁿ )_ti (AnINORG^q~)_t2 (II-IonLiqu) wherein

AnINORG^q is an anion selected from the group consisting of BF₄ , PF₆ , CF₃SO₃ , (CF₃S0₂)₂N , (FS0₂)₂N , anions of Ci_₂o monocarboxylic aliphatic acids, N(CN)₂ , C(CN)₃ , B(CN)₄ , and mixtures thereof; and

CatINORGⁿ is selected from the group consisting of Li⁺, Na⁺, K⁺, Ag⁺, Mg²⁺, Zn²⁺, Ca²⁺,

Ba²⁺, H₃0⁺ and H₅0₂ ⁺;

n is 1 or 2;

q is 1;

tl is 1;

t2 is 1 or 2;

when n is 1 and q is 1, then tl is 1 and t2 is 1;

when n is 2 and q is 1 , then tl is 1 and t2 is 2.

22. Electrolyte formulation (ElFormul) according to claim 19, wherein

Catⁿ⁺ in compound of formula (I-Cat-n) is selected from the group consisting of

CatORG-B⁺,

C₄H_{9 ? Li}+_{? Na}+_{? K}+_{? Mg}2+ _{and Zn}2+. AnINORG^q in compound of formula (I-Cat-n) is selected from the group consisting of PF₆ ,

(CF₃S0₂)₂N^~, (FS0₂)₂N^~ and B(CN)₄ ^";

n is 1 or 2;

q is 1;

tl is 1;

t2 is 1 or 2;

when n is 1 and q is 1, then tl is 1 and t2 is 1; when n is 2 and q is 1 , then tl is 1 and t2 is 2;

n+

CatORG-B is selected from the group consisting of 1,3-dimethylimidazolium, l-ethyl3- methylimidazolium, l-propyl-3 -methylimidazolium, l-allyl-3 -methylimidazolium, 1- methyl-3-hexyl imidazolium, 1-ethylimidazolium, l-butyl-2,3-dimethylimidazolium and mixture thereof.

23. Electrolyte formulation (ElFormul) according to one or more of claims 16 to 22, which comprises a redox couple (RedOxCoup), wherein

redox couple (RedOxCoup) is selected from the group consisting of Br /Br₂, 1 /I₃, SCN7SCN₂, SeCN^~/SeCN₂ and bipyridine cobalt (III/II);

24. Electrochemical or an optoelectronic device (ElDev) which comprises the electrolyte formulation (ElFormul) as defined in one or more of claims 16 to 23.