WO2014147162A1

WO2014147162A1 - Tricyano(fluorophenyl)borates

Info

Publication number: WO2014147162A1
Application number: PCT/EP2014/055568
Authority: WO
Inventors: Stefan Ellinger; Lothar Ott; Christiaan RIJKSEN; Florencio Zaragoza Doerwald; Govert VERSPUI; Thomas Jagusch; Ginger LUTTEKE
Original assignee: Lonza AG
Current assignee: Lonza AG
Priority date: 2013-03-21
Filing date: 2014-03-20
Publication date: 2014-09-25
Anticipated expiration: 2015-09-21

Abstract

The invention discloses tricyano(fluorophenyl)borates, a method for their preparation and their use as ionic liquid.

Description

TRICYANO(FLUOROPHENYL)BORATES

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, 1 12, 3926-3945.

Ionic liquids have a series of interesting properties: Usually, they are thermally stable, relatively non-flammable and have a low vapour 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.

WO 2010/086131 A discloses tricyanoborates of the general formula

Catⁿ [B(CN)3(XRl)]ⁿ and their use as ionic liquids, wherein Rl is inter alia Ci_₆ alkyl or benzyl; X is inter alia oxygen; and Catⁿ is a cation, which is selected from the group consisting of an inorganic cation and an organic cation; with n being 1 or 2. Rl is not substituted by halogen. WO2012/041434 discloses electrolyte formulations containing borate anions of formula

[B(CN)3(OR*)], their preparation and their use, in particular as part of electrolyte

formulations for electrochemical or optoelectronic devices. R* denotes straight-chain or branched alkyl groups having 1 to 12 C atoms which can be partially subsituted by Hal and Hal denotes F, CI, Br or I.

There was a need for stable compounds which can be used as ionic liquids or as precursors of ionic liquids. These compounds should be able to be disposed of in an environmentally friendly manner after use. They should show good performance in applications for ionic liquids, e.g. such as dye sensitized solar cells.

This task object is achieved by tricyano(fluorophenyl)borates.

Unexpectedly, the compounds of instant invention show good efficiency in dye sensitized solar cells.

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_6-1o 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_i₀ 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);

DCM dichloromethane;

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;

IL ionic liquid;

"linear" and "n-" are used synonymously with respect to the respective isomers of alkanes; RT room temperature, it is used synonymously with the expression ambient

temperature;

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

"wt%", "% by weight" and "weight-%" are used synonymously and mean percent by weight.

SUMMARY OF THE INVENTION

Subject of the invention is a compound of formula (I);

wherein

n+

Cat is a cation, which is selected from the group consisting of inorganic cation

CatINORGⁿ⁺ and organic cation CatORGⁿ⁺;

(A) in formula (I) is an aromatic ring selected from the group consisting of phenyl and naphthyl;

n is 1 or 2;

m is 1, 2, 3, 4 or 5 when (A) is phenyl;

m is 1, 2, 3, 4, 5, 6 or 7 when (A) is naphthyl;

g

s in the residue R is, in case that (A) is phenyl, an integer from 1 to (5 - m) with the proviso, that if m is 5 then s is 0;

g

s in the residue R is, in case that (A) is naphthyl, an integer from 1 to (7 - m) with the proviso, that if m is 7 then s is 0;

R is,

in case of (A) being phenyl and of m being 1 , 2 or 3 independently from any other R^s,

in case of (A) being nahpthyl and of m being 1, 2, 3, 4 and 5 independently from any g

other R ,

selected from the group consisting of H, CI, Br, I, Ci_₄ alkyl, C₅_₆ cycloalkyl, C₂_₄ alkene, (CF₂)_t5-F, Ci_₄ alkoxy,

, phenyl, perfiuorophenyl, benzyl, C(H)0, C(0)Ci_₄ alkyl, [(CH₂)₂_₄-0]_ti-Ci_₄ alkyl, [(CH₂C(H)(CH₃)-0]_t2-C₁_4 alkyl, [(C(H)(CH₃)-CH₂-0]t₃-d_4 alkyl, N0₂, N(d_₄ alkyl)₂, N(Ci_₄ alkyl) C(O) Ci_₄ alkyl), CN, N(Ci_₄ alkyl) C(0)-0- Ci_₄ alkyl, N(CN)₂, 0-C₆H₅, O-C(O) Ci_₄ alkyl, 0-C(0)-C₆H₅, S-Ci_₄ alkyl, S(0)₂(Ci_₄ alkyl),

S(0)₂(0-Ci_₄ alkyl) and 0-S(0)₂(Ci_₄ alkyl);

tl, t2 and t3 are identical or different and independently from each other in integer from 1 to 5;

t4 is 2 to 6;

t5 is 1 to 6;

any alkyl and any cycloalkyl residue is unsubstituted or a perfluoro alkyl or a

perfluorocycloalkyl residue or is substituted by 1 , 2 or 3 identical or different substituents independently from each other selected from the group consisting of F, CI, Br, perfluoro Ci_₄ alkyl, perfluoro Ci_₄ alkoxy, perfluoro S-Ci_₄ alkyl,

unsubstituted Ci_₄ alkyl, Ci_₄ alkoxy, S-Ci_₄ alkyl, unsubstituted N(Ci_₄ alkyl), C(H)0 and unsubstituted C(O) Ci_₄ alkyl;

(*) denotes the bond to the ring (A).

DETAILED DESCRIPTION OF THE INVENTION

The value of s therefore is dependent on the value of m:

When m is 1 then

s is 1, 2, 3 or 4 in case of (A) being phenyl and s denotes the substituents R¹, R², R³ and

R⁴, and

s is 1, 2, 3, 4, 5 or 6 in case of (A) being naphthyl and s denotes the substituents R¹, R², R³, R⁴, R⁵ and R⁶;

when m is 2 then

s is 1, 2 or 3 in case of (A) being phenyl and s denotes the substituents R¹, R² and R³, and s is 1, 2, 3, 4 or 5 in case of (A) being naphthyl and s denotes the substituents R¹, R², R³, R⁴ and R⁵;

when m is 3 then

s is 1 or 2 in case of (A) being phenyl and s denotes the substituents R¹ and R², and s is 1, 2, 3 or 4 in case of (A) being naphthyl and s denotes the substituents R¹, R², R³ and

R⁴;

when m is 4 then

s is 1 in case of (A) being phenyl and s denotes the substituent R¹, and

s is 1, 2 or 3 in case of (A) being naphthyl and s denotes the substituents R¹, R² and R³; when m is 5 then

g

s is 0 in case of (A) being phenyl and no substituent R exists, and

s is 1 or 2 in case of (A) being naphthyl and s denotes the substituents R¹ and R²;

when m is 6 in case of (A) being naphthyl, then

s is 1 and s denotes the substituent R¹;

when m is 7 in case of (A) being naphthyl then

g

s is 0 and no substituent R exists.

Preferably, CatlNORG is selected from the group consisting of Li , Na , K , Rb , Cs , NH₄ ⁺, Ag⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺;

more preferably, CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, NH₄ ⁺, Ag⁺, Mg²⁺, and Ca²⁺;

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

especially, CatINORGⁿ⁺ is Li⁺, Na⁺, K⁺ or Ag⁺; more especially, CatINORGⁿ is Li⁺ or K⁺.

Preferably, CatORG contains a heteroatom selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen;

mor^•ee pprreeffeerraabbllyy,, CCaattOORRGGⁿ⁺ c contains a heteroatom selected from the group consisting of nitrogen and phosphorus.

When n is 2, then CatORG is preferably (H₃N-CH2-CH2-NH₃)²⁺.

Preferably, n in CatORG is 1.

When n is 1 , then CatORG is preferably 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;

(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, C_3-10 cycloalkyl and C₆-io aryl, with the proviso, that at least one of the residues R2, R3, R4 and R5 is not H; or

(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_₂o alkyl, Ci_₂o perfluoroalkyl, C3-10 cycloalkyl and C₆-io 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_₂o alkyl, Ci_₂o perfluoroalkyl,

C3-10 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,

C₃_io 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 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_s alkyl or Ci_8 perfluoroalkyl.

The term "where applicable" means e.g., that any of the 1, 2 or 3 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 a substituents.

More preferably, 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, l,2,3-tris(diethylamino)cyclopropenylium,

l,2,3-tris(trimethylsilyl)cyclopropenylium and tropylium,

1,2,3, 4,5, 6,7-heptaphenylcyclohepta-2,4,6-trien-l-ylium. Even more preferably, CatORGⁿ⁺ is selected from the group consisting of

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

R20 is Ci_2o alkyl;

R21, R22 and R23 are identical or different and independently selected from the group consisting of H and C_1-20 alkyl; preferably,

R20 is Ci-14 alkyl;

R21, R22 and R23 are identical or different and independently selected from the group consisting of H and C_1-14 alkyl; more preferably,

R20 is Ci_8 alkyl;

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

Especially, CatORGⁿ⁺ is selected from the roup consisting of

ε₂ΗΓ^{Ν/ Ν}-Η

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

3

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

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

In another more preferable embodiment, CatORG is

. wherein

R20 is Ci_₂₀ alkyl;

R21 is H and Ci_₂o alkyl;

preferably,

R20 is Ci.14 alkyl;

R21 is H and C i_i ₄ alkyl;

more preferably,

R20 is Ci_8 alkyl;

R21 is H and Ci_8 alkyl;

even more preferably,

R20 is methyl and R21 is ethyl.

In particular,

CatlNORG is Li or K ;

CatORG is

R20 is methyl and R21 is ethyl.

Preferably,

when (A) is phenyl then

m is 1, 2, 4 or 5, and

s is an integer from 1 to (5 - m) with the proviso, that if m is 5 then s is 0, and s s

R is, in case of m being 1 or 2 independently from each other R , selected from the

H, CI, Br, methyl, ethyl, methoxy, ethoxy, CF₃ and phenyl;

when (A) is naphthyl then

m is 7; more preferably,

when (A) is phenyl then

m is 1, 2, 4 or 5, and

s is an integer from 1 to (5 - m) with the proviso, that if m is 5 then s is 0, and

S S

H, CI, Br, methyl, ethyl, methoxy, ethoxy, CF₃ and phenyl;

when (A) is naphthyl then

m is 7: even more preferably,

when (A) is phenyl then

m is 1, 2, 4 or 5, and

R^S is H;

when (A) is naphthyl then

m is 7; especially, compound of formula (I) is selected from the group consisting of compound of formula (I-lo), compound of formula (I-lp), compound of formula (1-2-6), compound of formula (1-2-3-5-6), compound of formula (I-penta), compound of formula (I-a-hepta) and compound of formula (I-b-hepta);

(I-penta)

(I-a-hepta)

(I-b-hepta)

with Catⁿ⁺ as defined above, also with all its preferred embodiments. More especially, compound of formula (I) is compound of formula (I-penta);

with Catⁿ⁺ as defined above, also with all its preferred embodiments.

Even more especially, compound of formula (I) is compound of formula (1) or compound of formula (2).

Further subject of the invention is a method for the preparation of compound of formula (I), the method comprises a step (Stl) or a step (St2);

step (Stl) comprises a reaction (Real), wherein compound of formula (Al) is reacted with trimethylsilylcyanide in the presence of cation Catⁿ ;

step (St2) comprises a reaction (Rea2), wherein a compound of formula (I-Cat-r)

is reacted with a compound of formula (I-Cat-n);

(Catⁿ )(AnINORG^q")t q is 1 or 2;

r is 1 or 2;

when n and q are identical, then t is 1 ;

when n is 2 and q is 1 , then t is 2;

when n is 1 and q is 2, then t is 0.5;

AnINORG^q 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 , Ci_6 alkylsulfonate, Ci_₆ alkylsulfate, dioctylsulfosuccinate, 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;

Cat-/ has the same definition as Catⁿ and is different from Catⁿ ;

rH^~ S

Cat , n, m, s, (A) and R are as defined above, also with all their preferred embodiments.

Preferably, in reaction (Real) cation Cat is present in form a compound (CYANS ALT) and compound (CYANS ALT) is [Catⁿ⁺][CN]_n, with Catⁿ⁺ and n as defined above, also with all their preferred embodiments;

more preferably, compound (CYANS ALT) is [CatINORGⁿ⁺][CN]„, with CatINORGⁿ⁺ and n as defined above, also with all their preferred embodiments;

even more preferably, compound (CYANS ALT) is [CatINORGⁿ⁺] [CN]„, and CatINORGⁿ⁺ is selected from the group consisting of Li , Na , K , NH₄ , Mg , and Ca , n is 1 or 2 respectively in this case;

espe jcciiaallllyy,, ccoommppoouunndd ((CCYYAA1NS ALT) is [CatlNORG ][CN]„, and CatlNORG is selected from the group consisting of Li^†, Na^†, K^† and NH₄ ^†, n is 1 respectively in this case; more especially, compound (CYANS ALT) is [CatINORGⁿ⁺][CN]„, and CatINORGⁿ⁺ is Na⁺ or K⁺, n is 1 respectively in this case.

Preferably, from 1.5 to 10 mol equivalents, more preferably from 3 to 5 mol equivalents, of trimethylsilylcyanide are used in reaction (Real), the mol equivalents being based on the mol of compound of formula (Al).

Preferably, from 0.8 to 5 mol equivalents, more preferably from 0.9 to 3 mol equivalents, even more preferably from 0.9 to 2 mol equivalents, of Catⁿ⁺, preferably in form of compound (CYANS ALT), are used in reaction (Real), the mol equivalents being based on the mol of compound of formula (Al).

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

For example, when the reaction product of reaction (Real) is a solid, it is preferably suspended in a solvent (SUSP), solvent (SUSP) is selected from the group consisting of heptane, DCM, acetonitrile and mixtures thereof;

then the obtained suspension is filtered and preferably washed. This extraction can be repeated with a different solvent (SUSP). Evaporation, preferably under vacuum, provides compound of formula (I).

Further preferred embodiments for purification are reversed phase column chromatography and dissolution and treatment of the solution with charcoal and filtration. Reaction (Rea2) is a metathesis reaction, also called a salt-exchange reaction, in which a first cation is replaced by a second cation.

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 , methyl sulfonate, ethyl sulfonate, methyl sulfate, ethyl sulfate, acetate, oleate, fumarate, maleate, oxalate, benzoate, N(CN)₂ , and mixtures thereof; more preferably, AnINORG^C| is an anion selected from the group consisting of CI , OH^", GST, sulfate, hydrogensulfate, C0₃ ^2", HC0₃ , acetate, and mixtures thereof.

Preferably in case of reaction (Rea2), a compound of formula (I) with Cat being CatORG is prepared in step (St2) by a reaction (Rea2), wherein a compound of formula (I-Cat-r), wherein Cat-/ has the definition of CatINORGⁿ , is reacted with 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 preferred embodiments. Preferably, when n and r are identical, then from 1 to 1.5 mol equivalents, more preferably from 1 to 1.2 mol equivalents, of compound of formula (I-Cat-n) are used in reaction (Rea2), the mol equivalents being based on the mol of compound of formula (I-Cat-r). Preferably, when n is 2 and r is 1, then from 0.5 to 0.75 mol equivalents, more preferably from 0.5 to 0.6 mol equivalents, of compound of formula (I-Cat-n) are used in reaction (Rea2), the mol equivalents being based on the mol of compound of formula (I-Cat-r).

Preferably, when n is 1 and r is 2, then from 2 to 3 mol equivalents, more preferably from 2 to 2.4 mol equivalents, of compound of formula (I-Cat-n) are used in reaction (Rea2), the mol equivalents being based on the mol of compound of formula (I-Cat-r).

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, C_5-10 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-Cat-r).

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 a 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, compound of formula (Al) is prepared in a step (StO);

step (StO) is done before step (Stl);

step (StO) comprises a reaction (ReaO), wherein BC1₃ is reacted with a compound of formula

(AO);

HQ

\

'm with m, s, (A) and R as defined above, also with all their preferred embodiments.

Preferably, from 3 to 6 mol equivalents, more preferably from 3 to 5 mol equivalents, of compound of formula (AO) are used in reaction (ReaO), the mol equivalents being based on the mol of BCl₃.

The reaction temperatures of reaction (ReaO) is preferably from -75 to 150 °C, more preferably from -50 to 100 °C, even more preferably from -50 to 50 °C.

Preferably, reaction (ReaO) is done is a solvent (SolO), solvent (SolO) is preferably selected from the group consisting of DCM, toluene, xylene and C5-10 alkane, more preferably solvent (SolO) is DCM.

C₅_io alkane is preferably pentane, hexane or heptane.

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

The reaction time of reaction (ReaO) is preferably from 30 min to 968 h, more preferably from 30 min to 48 h, even more preferably from 30 min to 24 h.

Preferably, reaction (ReaO) 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.

Compound of formula (AO) can be isolated after reaction (ReaO), preferably by distillation or sublimation. Further subject of the invention is the use of compound of formula (I), with compound of formula (I) as defined above, also with all its preferred embodiments,

preferably of compound of formula (I) with Catⁿ being CatORGⁿ , as solvent, preferably as solvent in inorganic 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, as electrolyte; as lubricant, as hydraulic fluid or as component in electrolyte formulations;

wherein such electrolyte formulations comprising a compound of formula (I), preferably a compound of formula (I) with Catⁿ being CatORGⁿ , are preferably used in electrochemical and/or optoelectronic devices;

wherein the electrochemical and/or optoelectronic devices are preferably selected from the group consisting of 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 a dye sensitized solar cell.

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-catalysed reactions, such as, for example, hydro formylation 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 plasticiser 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, working fluids for 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. Further subject of the invention is the use of compounds of formula (I), with compound of formula (I) as defined above, also with all its preferred embodiments, preferably of compounds of formula (I) with Catⁿ being CatORGⁿ , in electrochemical and/or optoelectronic devices, especially in electrolyte formulations in such electrochemical and/or optoelectronic devices, preferably as electrolyte in such electrochemical and/or optoelectronic devices.

Electrolyte formulations comprising a compound of formula (I), preferably a compound of formula (I) with Catⁿ being CatORGⁿ , can be preferably used in batteries, preferably in primary batteries and secondary batteries, in capacitors, in supercapacitors or in

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 , are 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) have low corrosivity towards metals, which simplifies their use and storage.

EXAMPLES

Methods

LCMS:

Agilent Instruments 1100 Series

Some mg of the compound were dissolved in MeCN, filtered over a 0.45 μιη Nylon filter and injected (1 μΐ) on a Waters XBridge (C18, 30 x 2.1mm, 3.5 μ) column.

Flow: 1 ml/min Column temp: 35°C

Eluent A: 0.1% formic acid in acetonitrile

Eluent B : 0.1% formic acid in water

Lin. Gradient: t = 0 min 2% A, t = 1.6 min 98% A, t = 3 min 98% A

Detection: DAD (220 to 320 nm)

Detection: MSD (ESI pos/neg) mass range: 100 to 800

Detection: NQAD (Quant QT-500) filter 1.3 sec; evaporation temperature: 35°C

Example 1: Synthesis of compound of formula (Al)

Pentafluorophenol (2.95 eq., 50 g) in DCM (80 ml) was added drop wise over 1.75 h to BC1₃ (1 eq., 1M in DCM) at -30°C. After stirring the reaction mixture for 4 hours at -30°C, the temperature was raised to ambient temperature under a flow of nitrogen over night. After concentration by distillation under reduced pressure, a grey white solid (48.52 g) was obtained. Sublimation with a bulb-to-bulb distillation apparatus (in German language:

KugelrohrdestiUationsapparatur) at 0.001 mbar at 120 to 130°C afforded 30 g (58%) of the desired compound of formula (Al) as a white solid. The purity is estimated at 85 to 90%> based on ¹⁹F-NMR analysis.

¹⁹F-NMPv (470.6 MHz, CD₂C1₂, TMS): delta [ppm] = -157.58 (d: J = 18.8 Hz); -162.08 (t: J =

18.8 Hz); -163.9 (t: J = 18.8 Hz)

1³C-NMR (100.6 MHz, CD₂C1₂, TMS): delta [ppm] = 127.4 to 127.6 (m); 137.2 to 137.6 (m);

137.8 to 138.1 (m); 139.6 to 139.8 (m); 140.4 to 140.6 (m); 142.1 to 142.3 (m).

"B-NMR (160.5 MHz, CD₂C1₂, TMS): delta [ppm] = 16.1 (s)

Example 2: Synthesis of compound of formula (1)

A suspension of compound of formula (Al) (25 g, 44.6 mmol, 1 eq., prepared according to example 1) and KCN (2.91 g, 44.6 mmol, 1.0 eq.) in TMSCN (15.5 g, 156 mmol, 3.5 eq.) was stirred at ambient temperature for 19 hours in a glass flask under argon atmosphere. The obtained brown suspension was concentrated (at a pressure of 0.004 Torr, bath temperature of 60°C for 3 h) to afford 15.2 g of a brown powder. This powder was purified with reversed phase column chromatography to afford 6.8 g of a brown powder, which was dissolved in water (136 mL) at ambient temperature. Then activated charcoal (6.8 g) was added. The mixture was stirred for 2 hours and filtered over Celite to afford a clear and slightly yellow solution. The residue was washed with water (136 mL) and the combined aqueous phase was freeze dried to afford 4.8 g (35%) of compound of formula (1) as an off white powder with a melting point (DSC) of ca. 193°C.

¹³C-NMR (100.6 MHz, CD₃CN, TMS): delta [ppm] = 126.7 (q: J = 75 Hz); 133.5 (m); 137.2

(double multiplet); 138.9 (double multiplet); 142.8 (double multiplet)

"B-NMR (128.3 MHz, CD₃CN, TMS): delta [ppm] = -19.35 (s)

¹⁹F-NMR (282.2 MHz, CD₃CN, TMS): delta [ppm] = -157.3 (d: J = 25 Hz); -166.8 (t: J = 25 Hz); -168.1 (t: J = 25 Hz)

LCMS [B(CN)3(OC6F5)]^": 272

Example 3: Synthesis of compound of formula (2)

To a suspension of compound of formula (1) (3 g, 9.65 mmol, 1 eq., prepared according to example 2) in CH₂CI₂ (42 mL) was added solid l-ethyl-3 -methyl- lH-imidazo Hum chloride (1.41 g, 9.65 mmol, 1.0 eq.) in a single portion. The suspension was stirred for 19 h at ambient temperature. Filtration over a glass filter (P4) afforded a light brown solid (890 mg) and a clear and slightly yellow organic phase. The solid residue was washed with CH₂CI₂ (42 mL) and the combined organic phase was concentrated on a rotary evaporator yielding 3.48 g (94%) of compound of formula (2) as a slightly yellow oil.

1H-NMR (400 MHz, CD₃CN, TMS): delta [ppm] = 1.47 (t, J = 8 Hz, 3H); 3.83 (s, 3H); 4.17

(q, J = 8 Hz, 3H); 7.34 (s, 1H); 7.40 (s, 1H); 8.50 (s, 1H)

1³C-NMR (100.6 MHz, CD₃CN, TMS): delta [ppm] = 15.4 (s); 36.7 (s); 45.8 (s); 122.9 (s);

126.5 (s); 126.7 (q: J = 74 Hz), 133.5 (m); 137.3 (double multiplet); 136.6 (s); 138.9

(double multiplet), 142.9 (double multiplet)

"B-NMR (128.3 MHz, CD₃CN, TMS): delta [ppm] = -19.4 (s)

¹⁹F-NMR (282.2 MHz, CD₃CN, TMS): delta [ppm] = -157.3 (d: J = 22.5 Hz); -166.8 (t: J = 22.5 Hz); -168.1 (t: J = 22.5 Hz) Application example

Compound were tested in dye sensitized solar cells and compared to the compound l-ethyl-3- methylimidazo Hum tricyanomethoxyborate, called COMP-W0131-Ex2, prepared according to example 2 of WO 2010/086131 Al.

DMII dimethylimidazoliumiodide

EMU ethylmethylimidazoliumiodide

EMI ethylmethylimidazolium

NBB n-butylbenzimidazol

GNCS guanidiniumthiocyanid

The compound tested is called compound(TEST), compound(TEST) is selected from the

group consisting of was compound of formula (2) and COMP-W0131-Ex2.

Device fabrication: Photoanodes 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 ΙΟΩ/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 sintererd 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 15Q/cm², 2 mm thick) on which the drop of a solution of hexachloroplatinate acid in n- propanol was cast. Thermal platinization occured 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:

electrolyte A = DMII/EMII/compound(TEST) /I₂/NBB/GNCS (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^"1, equivalent of 1 sun at air mass global, AM 1.5G, 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 lockin 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 (10% 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 tables 1 and 2 at 0.1 sunlight.

The tables show the photovoltaic parameters of CI 06 dye based devices measured under irradiation of 10 mW cm-2 AM 1.5G Sunlight.

The higher the efficiency the better.

Table 1 : results of COMP-WO 131 -Ex2

Table 2: results of compound of formula (2)

J_sc short circuit photo current

V_oc open circuit voltage

FF fill factor

η efficiency

Claims

1. Compound of formula (I);

wherein

n+

CatINORGⁿ⁺ and organic cation CatORGⁿ⁺;

n is 1 or 2;

m is 1 , 2, 3, 4 or 5 when (A) is phenyl;

m is 1 , 2, 3, 4, 5, 6 or 7 when (A) is naphthyl;

s is, in case that (A) is phenyl, an integer from 1 to (5 - m) with the proviso, that if m is

5 then s is 0;

s is, in case that (A) is naphthyl, an integer from 1 to (7 - m) with the proviso, that if m is 7 then s is 0;

R^S is,

in case of (A) being nahpthyl and of m being 1 , 2, 3, 4 and 5 independently from g

any other R ,

selected from the group consisting of H, CI, Br, I, Ci_₄ alkyl, C5-6 cycloalkyl, C₂_₄ alkene, (CF₂)_t5-F, Ci_₄ alkoxy,

, phenyl, perfiuorophenyl, benzyl, C(H)0, C(0)Ci_₄ alkyl, [(CH₂)₂-₄-0]_ti-Ci_₄ alkyl,

[(CH₂C(H)(CH₃)-0]_t2-C₁_₄ alkyl, [(C(H)(CH₃)-CH₂-0]_t3-d_₄ alkyl, N0₂, N(C_1-4 alkyl)₂, N(Ci_₄ alkyl) C(O) Ci_₄ alkyl), CN, N(Ci_₄ alkyl) C(0)-0- Ci_₄ alkyl, N(CN)₂, 0-C₆H₅, O-C(O) Ci_₄ alkyl, 0-C(0)-C₆H₅, S-Ci_₄ alkyl, S(0)₂(Ci_₄ alkyl),

S(0)₂(0-Ci_₄ alkyl) and 0-S(0)₂(Ci_₄ alkyl);

t4 is 2 to 6;

t5 is 1 to 6;

any alkyl and any cycloalkyl residue is unsubstituted or a perfluoro alkyl or a

(*) denotes the bond to the ring (A).

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

CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, Ag⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺.

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

CatORGⁿ⁺ contains a heteroatom selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen.

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

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

5. Compound of formula (I) according to one or more of claim 1, 3 and 4, wherein when n is 1, then CatORG⁺ is preferably 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;

(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_₂o alkyl, Ci_₂o perfluoroalkyl, C3-io-cycloalkyl and C₆-io aryl; or

CatOrg-B⁺ is (XR6R7R8)⁺,

wherein

X is nitrogen,

C3-io-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_₂₀ alkyl, Ci_₂₀ perfluoroalkyl,

C3-10 cycloalkyl and C₆-io aryl; or

C3-10 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;

in case of 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_s alkyl or Ci_8 perfluoroalkyl.

6. Compound of formula (I) according to one or more of claim 1 , 3, 4 and 5, wherein

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, l ,2,3,4,5,6,7-heptaphenylcyclohepta-2,4,6-trien-l-ylium.

7. Compound of formula (I) according to one or more of claim 1 , 3, 4, 5 and 6, wherein CatORG is

selected from the group consisting of R22

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

R20 is Ci_2o alkyl;

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

8. Compound of formula (I) according to one or more of claims 1 to 7, wherein when (A) is phenyl then

m is 1 , 2, 4 or 5, and

S S

R is, in case of m being 1 or 2 independently from each other R , selected from the H, CI, Br, methyl, ethyl, methoxy, ethoxy, CF₃ and phenyl;

when (A) is naphthyl then

m is 7.

9. Compound of formula (I) according to one or more of claims 1 to 8, wherein compound of formula (I) is selected from the group consisting of compound of formula (I-lo), compound of formula (I-lp), compound of formula (1-2-6), compound of formula (1-2-3-5-6), compound of formula (I-penta), compound of formula (I-a-hepta) and compound of formula (I-b-hepta).

(I-penta)

(I-a-hepta)

(I-b-hepta)

10. Compound of formula (I) according to one or more of claims 1 to 9, wherein compound of formula (I) is compound of formula (I-penta).

11. Compound of formula (I) according to one or more of claims 1 or 10, wherein compound of formula (I) is compound of formula (1) or compound of formula (2).

12. Method for the preparation of compound of formula (I) as defined in claim 1, the method comprises a step (Stl) or a step (St2);

step (St2) comprises a reaction (Rea2), wherein a compound of formula (I-Cat-r)

is reacted with a compound of formula (I-Cat-n);

(Catⁿ )(AnINORG^q")t q is 1 or 2;

r is 1 or 2;

when n and q are identical, then t is 1 ;

when n is 2 and q is 1 , then t is 2; when n is 1 and q is 2, then t is 0.5;

(CF₃S0₂)₂N , (FS0₂)₂N , Ci_6 alkylsulfonate, Ci_₆ alkylsulfate, dioctylsulfosuccinate, 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;

Cat-/ has the same definition as Catⁿ and is different from Catⁿ ;

rH^~ S

Cat , n, m, s, (A) and R are as defined in claim 1.

13. Method according to claim 12, wherein

in reaction (Real) cation Catⁿ is present in form a compound (CYAN SALT) and compound (CYANS ALT) is [Catⁿ⁺][CN]„, with Catⁿ⁺ and n as defined in claim 1.

14. Method according to claim 13, wherein

compound (CYANS ALT) is [CatINORGⁿ⁺][CN]_n, with CatINORGⁿ⁺ as defined in claim 1 or 2.

15. Method according to claim 13 or 14,

compound (CYANSALT) is [CatINORGⁿ⁺] [CN], and CatINORGⁿ⁺ is selected from the group consisting of Li , Na , K , NH₄ , Mg , and Ca .

16. Method according to one or more of claims 12 to 15, wherein

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^~, methyl sulfonate, ethyl sulfonate, methyl sulfate, ethyl sulfate, acetate, oleate, fumarate, maleate, oxalate, benzoate, N(CN)₂ , and mixtures thereof.

17. Method according to one or more of claims 12 to 16, wherein

compound of formula (Al) is prepared in a step (StO); step (StO) is done before step (Stl);

step (StO) comprises a reaction (ReaO), wherein BC1₃ is reacted with a compound of formula (AO);

HQ

(F)_m g

with m, s, (A) and R as defined in claim 12.

18. Use of compound of formula (I) as defined in claim 1 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, as component in electrolyte formulations.

19. Use according to claim 18 of compound of formula (I) as component in electrolyte

formulations, wherein

such electrolyte formulations comprising a compound of formula (I) are used in batteries, in capacitors, in supercapacitors or in electrochemical cells.

20. Use according to claim 18 of compound of formula (I) as component in electrolyte

formulations, wherein

such electrolyte formulations comprising a compound of formula (I) are used in

electrochemical and/or optoelectronic devices.

21. Use according to claim 20 of compound of formula (I), wherein the electrochemical and/or optoelectronic devices are selected from the group consisting of photovoltaic cell, light emitting device, electrochromic or photo-electrochromic device, electrochemical sensor and/or biosensor and dye sensitized solar cell.