Electrochromic materials; preparation and use thereof

A method of forming an electrochromic film, comprising,

• providing a solution or homogeneous suspension comprising a salt;
• a solvent;
• a small molecule organic electrochromic material of formula (I), (I-A), (II), (II-A), (III), or a combination thereof;
• a polymer or copolymer electrochromic of formula (IV), (V), (V-A), (VI), (VI-A), or a combination thereof;
• and optionally a plasticizer;
• and
• forming an electrochromic film from the solution or suspension,
• wherein the small molecule organic electrochromic material of formula (I), (I-A), (II), (II-A), (III), and polymer or copolymer electrochromic of formula (IV), (V), (V-A), (VI), (VI-A) have the structures:
• wherein
• each X1 independently is O, S, or NR;
• R is H, C1-20 alkyl;
• each R1 independently is C1-20 alkyl;
• each Z1 independently is H, C1-20 alkyl, halogen, nitro, cyano, hydroxyl, C6-C12 aryl, C3-C20 cycloalkyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C1-C20 haloalkyl, amino, C1-C12 alkylamino, or C1-C12 diaminoalkyl;
• Ar is anthracene, benzophenone, 2,1,3-benzothiadiazole, dibenzofuran, dibenzothiophene, diphenylfulvene, 1,3-diphenylisobenzofuran, 2,2′-dipyridyl, 4,4′-dipyridyl, fluorene, fluorenone, naphthyl, 2-nitrobiphenyl, phenanthrene, phenyl, pyrene, terphenyl, or triphenylene;
• each Z2 independently is C1-20 alkyl, halogen, nitro, cyano, hydroxyl, C6-C12 aryl, C3-C20 cycloalkyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C1-C20 haloalkyl, amino, C1-C12 alkylamino, or C1-C12 diaminoalkyl;
• q is 0, 1, 2, 3, or 4;
• Ar1 and Ar2 each independently is an aromatic group;
• each X2 independently is O, S, or NR;
• each R2 and R3 independently is
• C1-20 alkylene, or
• a poly(alkylene ether), a poly(alkylene glycol) comprising ethyleneoxy, propyleneoxy, and butyleneoxy repeating units containing 2-20 carbon atoms, or
• a C4-40 alkylene chain wherein the chain comprises 1, 2, 3, or 4 Q1 groups within the backbone of the chain, wherein each Q1 independently is O, S, —O(C═O)—, —(O═C)O—, —S(C═O)—, or —(O═C)S—;
• a is about 1 to about 99 mol %;
• b is about 1 to about 99 mol %;
• n is an integer resulting in a polymer or copolymer molecular weight of about 10,000 to about 100,000 g/mol;
• and
• wherein the salt comprises an alkali metal ion M, wherein the salt is is MClO4, MPF6, MBF4, MAsF6, MSbF6, MCF3SO3, MCF3CO2, M2C2F4(SO3)2, MN(CF3SO2)2, MN(C2F5SO2)2, MC(CF3SO2)3, MCnF2n+1SO3 wherein 2≤n≤3, MN(RfOSO2)2 wherein Rf is a fluoroalkyl group, or a combination thereof, or wherein the salt is an ionic liquid based on imidazolium, pyridinium, phosphonium or tetraalkyl ammonium.

An electrochromic device comprising:

• an electrochromic layer comprising an electrochromic material composition, and
• an electrolyte layer,
• wherein the electrochromic layer is adjacent to the electrolyte layer;
• wherein the electrochromic material composition comprises a salt, wherein the salt comprises an alkali metal ion M, wherein the salt is MClO4, MPF6, MBF4, MAsF6, MSbF6, MCF3SO3, MCF3CO2, M2C2F4(SO3)2, MN(CF3SO2)2, MN(C2F5SO2)2, MC(CF3SO2)3, MCnF2n+1SO3 wherein 2≤n≤3, MN(RfOSO2)2 wherein Rf is a fluoroalkyl group, or a combination thereof, or wherein the salt is an ionic liquid based on imidazolium, pyridinium, phosphonium or tetraalkyl ammonium;
• a small molecule organic electrochromic material of formula (I), (I-A), (II), (II-A), or (III), or a combination thereof;
• and a polymer or copolymer electrochromic of formula (IV), (V), (V-A), (VI), or (VI-A), or a combination thereof;
• wherein
• wherein
• each X1 independently is O, S, or NR;
• R is H, C1-20 alkyl;
• each R1 independently is C1-20 alkyl;
• each Z1 independently is H, C1-20 alkyl;
• halogen, nitro, cyano, hydroxyl, C6-C12 aryl, C3-C20 cycloalkyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C1-C20 haloalkyl, amino, C1-C12 alkylamino, or C1-C12 diaminoalkyl;
• Ar is an aromatic group, specifically anthracene, benzophenone, 2,1,3-benzothiadiazole, dibenzofuran, dibenzothiophene, diphenylfulvene, 1,3-diphenylisobenzofuran, 2,2′-dipyridyl, 4,4′-dipyridyl, fluorene, fluorenone, naphthyl, 2-nitrobiphenyl, phenanthrene, phenyl, pyrene, terphenyl, or triphenylene;
• each Z2 independently is C1-20 alkyl, halogen, nitro, cyano, hydroxyl, C6-C12 aryl, C3-C20 cycloalkyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C1-C20 haloalkyl, amino, C1-C12 alkylamino, or C1-C12 diaminoalkyl;
• q is 0, 1, 2, 3, or 4;
• Ar1 and Ar2 each independently is an aromatic group;
• each X2 independently is O, S, or NR;
• each R2 and R3 independently is
• C1-20 alkylene, or
• a poly(alkylene ether), a poly(alkylene glycol) comprising ethyleneoxy, propyleneoxy, and butyleneoxy repeating units containing 2-20 carbon atoms, or
• a C4-40 alkylene chain wherein the chain comprises 1, 2, 3, or 4 Q1 groups within the backbone of the chain, wherein each Q1 independently is O, S, —O(C═O)—, —(O═C)O—, —S(C═O)—, or —(O═C)S—;
• a is about 1 to about 99 mol %;
• b is about 1 to about 99 mol %;
• and
• n is an integer resulting in a polymer or copolymer molecular weight of about 10,000 to about 100,000 g/mol;
• and
• wherein the electrochromic material composition optionally further comprises a plasticizer, a solvent, or a combination thereof.