Malononitrile-derivative anion salts, and their uses as ionic conducting materials

Ionic compound derived from malononitrile having an anionic part associated to at least one cationic part Mm+ in sufficient number to provide electronic neutrality of the assembly, wherein M is an organic cation having a valency m selected from the group consisting of a diaryliodonium cation, a dialkylaryliodonium cation, a triarylsulfoniumn cation, a trialkylaryl sulfonium cation, an hydroxonium, a nitrosonium NO+, an ammonium —NH4+, a metallic cation having a valency m, an organic cation having a valency m or an organometallic cation having a valency m, and a substituted or non-substituted phenacyl-dialkyl sulfonium cation, and that the anionic part corresponds to one of the formula RD—Y—C(C≡N)2− or Z—C(C≡N)2− in which:

• Z represents an electroattractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from:
• j) —CN, —NO2, —SCN, —N3, FSO2—, —CF3, R′FCH2— (R′F being a perfluorinated radical) fluoroalkyloxy, fluoroalkylthioxy, fluoroalkenyloxy, fluoroalkenylthioxy radicals;
• jj) radicals having at least one aromatic nuclei, unsubstituted or substituted with at least one nitrogen, oxygen, sulfur and a phosphorus atom, said nuclei being one of a not condensed nuclei and a condensed nuclei and said nuclei being unsubstituted or substituted with at least one substituent selected from halogens, —CN, —NO2, —SCN, —N3, CF2═CF—O—, radicals, RF— and RFCH2— in which RF represents at least one of a perfluoroalkyl radical having 1 to 12 carbon atoms, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxaalkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, and thia-alkenyl radicals, polymer radicals, radicals having at least one of:
• at least one cationic ionophoric group and at least one anionic ionophoric group;
• with the proviso that one substituent Z is a monovalent radical, a multivalent radical, or part of a multivalent radical carrying at least one group —C(C≡N)2, or at least one recurring unit of a polymer;
• Y represents a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfinyl group or a phosphonyl group and:
• RD is a radical selected from:
• a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, mono or polycyclic alicyclic or heterocyclic radicals;
• b) alkyl or alkenyl radicals having at least one functional group selected from ether, thioether, amine, imine, amide, carboxyl, carbonyl, isocyanate, isothiocyanate, or hydroxy groups;
• c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which one of the aromatic nuclei and at least one substituent of the nucleus has heteroatoms selected from nitrogen, oxygen, or sulfur;
• d) radicals having condensed aromatic cycles which have at least one of no heteroatom and a heteroatom selected from nitrogen, oxygen, or sulfur;
• e) halogenated or perhalogenated alkyl, alkenyl, aryl, alylalkyl, alkylaryl radicals, said radicals unsubstituted or substituted with a functional group selected from ether, thioether, imine, amine, carboxyl, carbonyl or hydroxy groups;
• f) radicals RCC(R′)(R″)—O— in which RC is an alkyl perfluorinated radical and R′ and R″ are independently from one another an hydrogen atom or a radical as defined in a), b), c) or d) above;
• g) radicals (RB)2N—, in which the radicals RH which are identical or different are one of the substituents defined in a), b), c), d) and e) above, or one of the RB being unsubstituted or substituted with a halogen atom, or the two radicals RB together with N form a ring;
• h) polymer radicals,
• i) radicals having at least one of:
• one or more cationic ionophoric, groups and one or more anionic ionophoric groups;
• with the proviso that one substituent RD is a monovalent radical, part of a multivalent radical carrying a plurality of —Y—C−(C≡N)2 groups or at least one recurring unit of a polymer;
• with the proviso that when Y is a carbonyl and RD is a perfluoroalkyl radical having 1 to 3 carbon atoms, or when Z is —CN, M is different from an alkali metal.

Ionic compound derived from malononitrile having an anionic part associated to at least one cationic part Mm+ in sufficient number to provide electronic neutrality of the assembly, wherein M is an organic cation having a valency m incorporating a 2,2′[azobis(2-2′-imidazolinio-2-yl)propane]2+ group or a 2,2′-azobis(2-amidiniopropane)2+ group, and that the anionic part corresponds to one of the formula RD—Y—C(C≡N)2− or Z—C(C≡N)2− in which:

• Z represents an electroattractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from:
• j) —CN, —NO2, —SCN, —N3, FSO2—, —CF3, R′FCH2— (R′F being a perfluorinated radical), fluoroalkyloxy, floroalkylthioxy, fluoroalkenyloxy, fluoroalkenylthioxy radicals;
• jj) radicals having at least one aromatic nuclei, which does or does not contain at least one nitrogen, oxygen, sulfur or phosphorus atom, said nuclei being one of a non condensed nuclei and a condensed nuclei and said nuclei being unsubstituted or substituted with at least one substituent selected from halogens, —CN, —NO2, —SCN, —N3, CF2═CF—O—, radicals, RF— and RFCH2— in which RF represents at least one of a perfluoroalkyl radical having 1 to 12 carbon atoms, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, and thia-alkenyl radicals, polymer radicals, radicals having at least one of at least one cationic ioniophoric group and at least one anionic ionophioric group;
• with the proviso that one substituent Z is a monovalent radical, a multivalent radical, or part of a multivalent radical carrying at least one group-C(C≡N)2, or at least one recurring unit of a polymer;
• Y represents a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfinyl group or a phosphonyl group and;
• RD is a radical selected from:
• a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, mono or polycyclic alicyclic or heterocyclic radicals;
• b) alkyl or alkenyl radicals having at least one functional group selected from ether, thioether, amine, imine, amide, carboxyl, carbonyl, isocyanate, isothiocyanate, or hydroxy groups;
• c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which one of the aromatic nuclei and at least one substituent of the nucleus has heteroatoms selected from nitrogen, oxygen, or sulfur;
• d) radicals having condensed aromatic cycles which have at least one of no heteroatom and a heteroatom selected from nitrogen, oxygen, or sulfur;
• e) halogenated or perhalogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl radicals, said radicals unsubstituted or substituted with a functional group selected from ether, thioether, imine, amine, carboxyl, carbonyl or hydroxy groups;
• f) radicals RCC(R′)(R″)—O— in which RC is an alkyl perfluorinated radical and R′ and R″ are independently from one another an hydrogen atom or a radical as defined in a), b), c) or d) above;
• g) radicals (RB)2N—, in which the radicals RB which are identical or different are one of the substituents defined in a), b), c), d) and e) above, or one of the RB being unsubstituted or substituted with a halogen atom, or the two radicals RB together with N form a ring;
• h) polymer radicals,
• i) radicals having at least one of:
• one or more cationic ionophoric groups and one or more anionic ionophoric groups;
• with the proviso that one substituent RD is a monovalent radical, part of a multivalent radical carrying a plurality of —Y—C−(C≡N)2 groups or at least one recurring unit of a polymer;
• with the proviso that when one of Y is a carbonyl and RD is a perfluoroalkyl radical having 1 to 3 carbon atoms, and when Z is —CN, M is different from an alkali metal.

Ionic compound derived from malononitrile having an anionic part associated to at least one cationic part Mm+ in sufficient number to provide electronic neutrality of the assembly, wherein M is an hydroxonium, a nitrosonium NO+, an ammonium —NH4+, a metallic cation having a valency m, an organic cation having a valency m or an organometallic cation having a valency m, and that the anionic part corresponds to one of the formula RD—Y—C(C≡N)2− and Z—C(C≡N)2− in which:

• Y represents a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfinyl group or a phosphonyl group;
• and
• RD is a radical selected from radicals having one or more anionic ionophoric groups consisting of a carboxylic function (—CO2−), a sulfonic function (—SO3−), a sulfonimide function (—SO2NSO2—) or a sulfonamide function (—SO2N);
• with the proviso that on substituent RD is a monovalent radical, part of a multivalent radical carrying a plurality of —Y—C−(C≡N)2 groups and at least one recurring unit of a polymer.

Ionic compound derived from malononitrile having an anionic part associated to at least one cationic part Mm+ in sufficient number to provide electronic neutrality of the assembly, wherein M is an hydroxonium, a nitrosonium NO+, an ammonium —NH4+, a metallic cation having a valency m, an organic cation having a valency m or an organometallic cation having a valency m, and that the anionic part corresponds to the formula RD—Y—C(C≡N)2− in which:

• Y represents a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfinyl group or a phosphonyl group;
• and
• RD is a radical selected from:
• a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, mono or polycyclic alicyclic or heterocyclic radicals;
• b) alkyl or alkenyl radicals having at least one functional group selected from ether, thioether, amine, imine, amide, carboxyl, carbonyl, isocyanate, isothiocyanate, or hydroxy groups;
• c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which one of the aromatic nuclei and at least one substituent of the nucleus has heteroatoms selected from nitrogen, oxygen, or sulfur;
• d) radicals having condensed aromatic cycles which have at least one of no heteroatom and a heteroatom selected from nitrogen, oxygen, or sulfur;
• e) halogenated or perhalogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl radicals, said radicals unsubstituted or substituted with a functional group selected from ether, thioether imine, amine, carboxyl, carbonyl and hydroxy groups;
• f) radicals RCC(R′)(R″)—O— in which RC is an alkyl perfluorinated radical and R′ and R″ are independently from one another an hydrogen atom or a radical as defined in a), b), c) or d) above;
• g) radicals (RB)2N—, in which the radicals RB which are identical or different are one of the substituents defined in a), b), c), d) and e) above, or one of the RB being unsubstituted or substituted with a halogen atom, or the two radicals RB together with N form a ring;
• h) polymer radicals,
• i) radicals having at least one of:
• one or more cationic ionophoric groups and one or more anionic ionophoric groups;
• with the proviso that one substituent RD is a monovalent radical, part of a multivalent radical carrying a plurality of —Y—C−(C≡N)2 groups and at least one recurring unit of a polymer;
• with the proviso that RD includes at least one ethylenic unsaturation and one of a condensable group and a group which is dissociable by one of thermal means, by photochemical means and by ionic dissociation.

Ionic compound derived from malononitrile having an anionic part associated to at least one cationic part Mm+ in sufficient number to provide electronic neutrality of the assembly, wherein M is an hydroxonium, a nitrosonium NO+, an ammonium —NII4+, a metallic cation having a valency m, an organic cation having a valency m or an organometallic cation having a valency m, and that the anionic part corresponds to the formula RD—Y—C(C≡N)2− in which:

• Y represents a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfinyl group or phosphonyl group;
• and
• RD is a radical selected from:
• a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, mono or polycyclic alicyclic or heterocyclic radicals;
• b) alkyl or alkenyl radicals having at least one functional group selected from ether, thioether, amine, imine, amide, carboxyl, carbonyl, isocyanate, isothiocyanate, or hydroxy groups;
• c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which one of the aromatic nuclei and at least one substituent of the nucleus has heteroatoms selected from nitrogen, oxygen, or sulfur;
• d) radicals having condensed aromatic cycles which does or does not contain a heteroatom selected from nitrogen, oxygen, or sulfur;
• e) halogenated or perhalogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl radicals, said radicals unsubstituted or substituted with a functional group selected from ether, thioether, imine, amine, carboxyl, carbonyl or hydroxy groups;
• f) radicals RCC(R′)(R″)—O— in which Rc is an alkyl perfluorinated radical and R′ and R″ are independently from one another an hydrogen atom or a radical as defined in a), b), c) or d) above;
• g) radicals (RB)2N—, in which the radicals RB which are identical or different are one of the substituents defined in a), b), c), d) and e) above, or one of the RB being unsubstituted or substituted with a halogen atom, or the two radicals RB together with N form a ring;
• h) polymer radicals,
• i) radicals having at least one of:
• one or more cationic ionophoric groups and one or more anionic ionophoric groups;
• with the proviso that one substituent RD is a monovalent radical, part of a multivalent radical carrying a plurality of —Y—C−(C≡N)2 groups or at least one recurring unit of a polymer;
• with the proviso that RD includes a group capable of trapping free radicals or a dissociating dipole.

Ionic compound derived from malononitrile having an anionic part associated to at least one cationic part Mm+ in sufficient number to provide electronic neutrality of the assembly, wherein M is an hydroxonium, a nitrosonium NO+, an ammonium —NH4+, a metallic cation having a valency m, an organic cation having a valency m or an organometallic cation having a valency m, and that the anionic part corresponds to the formula RD—Y—C(C≡N)2− in which:

• Y represents a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfinyl group or a phosphonyl group;
• and
• RD is a radical selected from:
• a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, mono or polycyclic alicyclic or heterocyclic radicals;
• b) alkyl or alkenyl radicals having at least one functional group selected from ether, thioether, amine, imine, amide, carboxyl, carbonyl, isocyanate, isothiocyanate, or hydroxy groups;
• c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which one of the aromatic nuclei and at least one substituent of the nucleus has heteroatoms selected from nitrogen, oxygen, or sulfur;
• d) radicals having condensed aromatic cycles which have at least one of no heteroatom and a heteroatom selected from nitrogen, oxygen, or sulfur;
• e) halogenated or perhalogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl radicals, said radicals unsubstituted or substituted with a functional group selected from ether, thioether, imine, amine, carboxyl, carbonyl or hydroxy groups;
• f) radicals RCC(R′)(R″)—O— in which RC is an alkyl perfluorinated radical and R′ and R″ are independently from one another an hydrogen atom or a radical as defined in a), b), c) or d) above;
• g) radicals (RB)2N—, in which the radicals RB which are identical or different are one of the substituents defined in a), b), c), d) and e) above, or one of the RB being unsubstituted or substituted with a halogen atom, or the two radicals RB together with N form a ring;
• h) polymer radicals,
• i) radicals having at least one of:
• one or more cationic ionophoric groups and one or more anionic ionophoric groups;
• with the proviso that RD represents a radical having a valency v higher than 2, including at both free ends a group —C(C≡N)2−;
• with the proviso that when Y is a carbonyl and RD is a perfluoroalkyl radical having 1 to 3 carbon atoms, or when Z is —CN, M is different from an alkali metal.