Pentacyclic anion salts or tetrazapentalene derivatives and their uses as ionic conducting materials

Process of modifying properties of solubility of a polymer having groups sensitive towards acids, characterized in that it consists in subjecting said polymer to actinic radiation or β radiation, in the presence of an ionically conductive material comprising an ionic compound in a solvent, the said compound comprising at least one anionic part associated to at least one cationic part M in sufficient number to ensure the electronic neutrality of the whole, wherein M is a hydroxonium, a nitosonium 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 in that the anionic part is pentacyclic or derived from tetrazapentalene and corresponds to one of the following formulae:

• in which the groups —Xi— represent independently from one another a group selected from —N═, —N—, —C(Yc)═, —C(Yc)—, —S(═O)(Qs)═, —S(Qs)═ or —P(Q′)(Q″)═, wherein among the five groups —Xi— forming the ring, no —Xi— represents —N═or —N−,or at least two —Xi— represent independently —N═or —N+—, at most four groups —Xi— comprise an hydrogen atom, at most two groups —Xi— comprise a sulfur atom provided they are not adjacent on the ring, at most one group —Xi— comprise a phosphorus atom, and:
• Q′ and Q″ represent independently from one another a C1-C8 perhaloalkyl or perhaloalkenyl radical a C6-C12 aryl or alkylaryl radical, optionally halogenated, each may contain oxa, thia, aza substituents;
• Qs is a radical selected from:
• a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic or heterocyclic radicals, including polycyclic radicals, said radicals being optionally halogenated or perhalogenated and/or optionally carrying at least one ether, thioether, amine, imine, amide, carboxyl, carbonyl, isocyanate, isothiocyanate, hydroxy functional group;
• b) monocyclic, polycyclic or condensed aromatic radicals in which the aromatic nuclei and/or at least one substituent of a nucleus comprise heteroatoms;
• c) polymer radicals;
• d) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups;
• Yc or Y represent II, or a group attracting electrons selected from the group consisting of:
• F, Cl, Br, —C≡N, —S—C≡N, —N═C═S, —N═C═O, —NO2, CnF2n+1—CnF2n+1—O—, CnF2n+1—CH2—, —OC2F4H, —SCF3, —SCnF2n+1, —SC2F4H, —O—CF═CF2, —SCF═CF2, FSO2;
• radicals QSO2—, —CO2Q, Q—N—SO2—, QCO—, in which Q is selected from the substituents defined above for Qs;
• radicals comprising one or more aromatic nuclei optionally containing at least one nitrogen, oxygen, sulfur or phosphorus atoms, said nuclei may optionally be condensed nuclei and/or the nuclei may optionally carry at least one substituent selected from halogens, —CN, —NO2, —SCN, —N3, CF2═CF—O—, radicals RF— and RFCH2— in which RF is a perfluoroalkyl radical having 1 to 12 carbon atoms, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxaalkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group;
• or two substituents selected from Yc, Qs, Q′ and Q″ of a pentacyclic anionic group on the one hand, or two substituents Y of an anionic group derived from tetrazapentalene on the other hand, together form a ring having 4 to 8 chains, said ring optionally being of aromatic conjugated nature;
• or one of the substituents Y, Yc or Qs is a multivalent radical (including a dendrimer) connected to at least another pentacyclic anionic group or to at least another anionic group derived from tetrazapentalene;
• or one of the substituents Y, Yc or Qs represent a recurring unit of a polymer.

A laser or optical disk containing a composition or photographic film having a sensitizer containing a composition in which the composition contains cationic coloring material, characterized in that it contains an ionically conductive material comprising an ionic compound, the said compound comprising at least one anionic part associated to at least one cationic part M in sufficient number to ensure the electronic neutrality of the whole, wherein M is a 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 in that the anionic part is pentacyclic or derived from tetrazapentalene and corresponds to one of the following formulae:

• in which the groups —Xi— represent independently from one another a group selected from —N═, —N—, —C(Yc )═, —C(Yc)—, —S(═O)(Qs)═, —S(Qs)═ or —P(Q′)(Q″)═, wherein among the five groups —Xi— forming the no —Xi— represents —N═or —N−,or at least two —Xi— represent independently —N═or —N+—, ring at most four groups —Xi— comprise an hydrogen atom, at most two groups —Xi— comprise a sulfur atom provided they are not adjacent on the ring, at most one group —Xi— comprise a phosphorus atom, and:
• Q′ and Q″ represent independently from one another a C1-C8 perhaloalkyl or perhaloalkenyl radical, a C6-C12 aryl or alkylaryl radical, optionally halogenated, each may contain oxa, thia, aza substituents;
• Qs is a radical selected from:
• a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic or heterocyclic radicals, including polycyclic radicals, said radicals being optionally halogenated or perhalogenated and/or optionally carrying at least one ether, thioether, amine, imine, amide, carboxyl, carbonyl, isocyanate, isothiocyanate, hydroxy functional group;
• b) monocyclic, polycyclic or condensed aromatic radicals in which the aromatic nuclei and/or at least one substituent of a nucleus comprise heteroatoms;
• c) polymer radicals;
• d) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups;
• Yc or Y represent H, or a group attracting electrons selected from the group consisting of:
• F, Cl, Br, —C≡N, —S—C≡N, —N═C═S, —N═C═O, —NO2, CnF2n+1—CnF2n+1—O—, CnF2n+1—CH2—, —OC2F4H, —SCF3, —SCnF2n+1, —SC2F4H, —O—CF═CF2, —SCF═CF2, FSO2;
• radicals QSO2—, —CO2Q, Q—N—SO2—, QCO—, in which Q is selected from the substituents defined above for Qs;
• radicals comprising one or more aromatic nuclei optionally containing at least one nitrogen, oxygen, sulfur or phosphorus atoms, said nuclei may optionally be condensed nuclei and/or the nuclei may optionally carry at least one substituent selected from halogens, —CN, —NO2, —SCN, —N3, CF2═CF—O—, radicals RF— and RFCH2— in which RF is a perfluoroalkyl radical having 1 to 12 carbon atoms, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxaalkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group;
• or two substituents selected from Yc, Qs, Q′ and Q″ of a pentacyclic anionic group on the one hand, or two substituents Y of an anionic group derived from tetrazapentalene on the other hand, together form a ring having 4 to 8 chains, said ring optionally being of aromatic conjugated nature;
• or one of the substituents Y, Yc or Qs is a multivalent radical (including a dendrimer) connected to at least another pentacyclic anionic group or to at least another anionic group derived from tetrazapentalene;
• or one of the substituents Y, Yc or Qs represent a recurring unit of a polymer.

Electrochrome device in which the electrolyte is an ionically conductive material comprising an ionic compound in a solvent, the said compound comprising at least one anionic part associated to at least one cationic part M in sufficient number to ensure the electronic neutrality of the whole, wherein M is a 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 in that the anionic part is pentacyclic or derived from tetrazapentalene and corresponds to one of the following formulae:

• in which the groups —Xi— represent independently from one another a group selected from —N═, —N—, C(Yc)═, —C(Yc)—, —S(═O)(Qs)═, —S(Qs)═ or —P(Q′)(Q″)═, wherein among the five groups —Xi — forming the ring, no —Xi— represents —N═ or —N−, or at least two —Xi— represent independently —N═ or —N+, at most four groups —Xi — comprise an hydrogen atom, at most two groups —Xi— comprise a sulfur atom provided they are not adjacent on the ring, at most one group —Xi— comprise a phosphorus atom, and:
• Q′ and Q″ represent independently from one another a C1-C8 perhaloalkyl or perhaloalkenyl radical, a C6-C12 aryl or alkylaryl radical, optionally halogenated, each may contain oxa, thia, aza substituents;
• Qs is a radical selected from:
• a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic or heterocyclic radicals, including polycyclic radicals, said radicals being optionally halogenated or perhalogenated and/or optionally carrying at least one ether, thioether, amine, imine, amide, carboxyl, carbonyl, isocyanate, isothiocyanate, hydroxy functional group;
• b) monocyclic, polycyclic or condensed aromatic radicals in which the aromatic nuclei and/or at least one substituent of a nucleus comprise heteroatoms;
• c) polymer radicals;
• d) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups:
• Yc or Y represent H, or a group attracting electrons selected from the group consisting of:
• F, Cl, Br, —C≡N, —S—C≡N, —N═C═S, —N═C═O, —NO2, CnF2n+1—CnF2n+1—O—, CnF2n+1—CH2—, —OC2F4H, —SCF3, —SCnF2n+1, —SC2F4H, —O—CF═CF2, —SCF═CF2, FSO2;
• radicals QSO2—, —CO2Q, Q—N—SO2—, QCO—, in which Q is selected from the substituents defined above for Qs;
• radicals comprising one or more aromatic nuclei optionally containing at least one nitrogen, oxygen, sulfur or phosphorus atoms, said nuclei may optionally be condensed nuclei and/or the nuclei may optionally carry at least one substituent selected from halogens, —CN, —NO2, —SCN, —N3, CF2═CF—O—, radicals RF— and RF CH2— in which RF is a perfluoroalkyl radical having 1 to 12 carbon atoms, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxaalkenyl, aza-alkyl, aza-alkenyl thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group;
• or two substituents selected from Yc Qs, Q′ and Q″ of a pentacyclic anionic group on the one hand, or two substituents Y of an anionic group derived from tetrazapentalene on the other hand, together form a ring having 4 to 8 chains, said ring optionally being of aromatic conjugated nature;
• or one of the substituents Y, Yc or Qs is a multivalent radical (including a dendrimer) connected to at least another pentacyclic anionic group or to at least another anionic group derived from tetrazapentalene;
• or one of the substituents Y, Yc or Qs represent a recurring unit of a polymer.