Electrolytes for electrooptic devices comprising ionic liquids
First Claim
Patent Images
1. An electrolyte solution having a Tg (glass transition temperature) of less than about −
- 40°
C., comprising at least one bifunctional redox dye dissolved in ionic liquid solvent.
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Abstract
Electrolyte solutions of soluble bifunctional redox dyes in molten salt solvent may be used to prepare electrooptic devices with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF3SO3−), bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N−), bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N−) and tris(trifluoromethylsulfonyl)methide ((CF3SO2)3C−).
117 Citations
23 Claims
-
1. An electrolyte solution having a Tg (glass transition temperature) of less than about −
- 40°
C., comprising at least one bifunctional redox dye dissolved in ionic liquid solvent. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10)
- 40°
-
11. An electro-optic device comprising at least one chamber and, as the electrolyte medium inside the chamber, an electrolyte solution having a Tg (glass transition temperature) of less than about −
- 40°
C. and comprising at least one bifunctional redox dye dissolved in an ionic liquid solvent. - View Dependent Claims (12, 13, 14, 15, 16, 17, 18, 19, 20)
- 40°
-
21. A compound having the structural formula
or having the structural formula or having the structural formula or having the structural formula wherein A− - is selected from the group consisting of trifluoromethylsulfonate (CF3SO3−
), bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N−
), bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N−
) and tris(trifluoromethylsulfonyl)methide ((CF3SO2)3C−
);
B−
is selected from the group consisting of a halogen anion, ClO4−
, BF4−
, PF6−
, AsF6−
, SbF6−
, CH3COO−
, and CH3(C6H4)SO3−
, trifluoromethylsulfonate (CF3SO3−
), bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N−
), bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N−
) and tris(trifluoromethylsulfonyl)methide ((CF3SO2)3C−
);
wherein R10 and R11 are each independently a hydrocarbon group selected from the group consisting of an alkyl, alkenyl and aryl group having 1 to 10 carbon atoms, in the case where R10 or R11 is an aryl group, the aryl group forms a condensed ring together with a cyclopentadienyl ring;
wherein m=0-4;
wherein n=0-4;
wherein R12 and R13 are each independently a hydrocarbon residue having 1 to 20 carbon atoms, or alkylene groups having ester-bond unit, ether-bond unit, amide-bond unit, thioether-bond unit, amine-bond unit, urethane-bond unit, or silyl unit in the part of hydrocarbon groups, and R14 is a hydrocarbon group selected from the group consisting of an alkyl, cycloalkyl, alkenyl, aryl, or aralkyl group having 1 to 20 carbon atoms, a heterocyclic group having 4 to 20 carbon atoms, and a substituted hydrocarbon or heterocyclic group obtained by substituting part of hydrogens of the hydrocarbon group or heterocyclic group with a substituent group; and
Me represents Cr, Co, Fe, Mn, Ni, Os, Ru, V, Mo(X)(Q), Nb(X)(Q), Ti(X)(Q), V(X)(Q)or Zr(X)(Q) wherein X and Q are each independently selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 12 carbon atoms, ClO4−
, BF4−
, PF6−
, AsF6−
, SbF6−
, CH3COO−
, CH3(C6H4)SO3−
, trifluoromethylsulfonate (CF3SO3−
), bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N−
), bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N−
) and tris(trifluoromethylsulfonyl)methide ((CF3SO2)3C−
);or having the formula
Cat1-An1,or having the formula
Cat1-Bridge1-An1,or having the formula
Cat1-Bridge1-An1-Bridge2-Cat2,or having the formula
An2-Bridge2-Cat1-Bridge1-An1,wherein Cat1-An1 represents a charge transfer complex; wherein Cat1 and Cat2 independently represent a radical having the structural formula or having the structural formula or having the structural formula or having the structural formula or having the structural formula or having the structural formula or having the structural formula or having the structural formula wherein R17 and R18 independently of one another denote C1 to C18-alkyl, C2 to C12-alkenyl, C3 to C7-cycloalkyl, C7 to C15-aralkyl or C6 to C10-aryl or R17 and R18 together form a —
(CH2)2—
, —
(CH2)3—
, or —
CH═
CH—
bridge, R19, R20 and R22 to R25 independently of one another denote hydrogen, C1 to C18-alkyl, C1 to C4-alkoxy, halogen, cyano, nitro or C1 to C18-alkoxycarbonyl or R22 and R23 and/or R24 and R25 form a —
CH═
CH—
CH═
CH—
bridge;
R26, R27, R28 and R29 independently of one another denote hydrogen or, in pairs, a —
(CH2)2—
, —
(CH2)3—
or —
CH═
CH—
bridge, E3 and E4 independently of one another denote O, N—
CN, C(CN)2 or N—
C6- to C10-aryl, R34 and R35 independently denote hydrogen, C1 to C18-alkyl, C1 to C18-alkoxy, halogen, cyano, nitro, C1 to C18-alkoxycarbonyl or C6 to C10-aryl, R30 to R33 independently of one another denote hydrogen or C1 to C6-alkyl, or R30 and R26 and/or R31 and R27 form a —
CH═
CH—
CH═
CH—
bridge, E1 and E2 independently of one another denote O, S, NR36 or C(R36)2 or E1 and E2 together form a —
N—
(CH2)2—
N—
bridge, R36 denotes C1 to C18-alkyl, C2 to C12-alkenyl, C4 to C7-cycloalkyl, C7 to C15-aralkyl or C6 to C10-aryl, Z1 denotes a direct bond, —
CH═
CH—
, —
C(CH3)═
CH—
, —
C(CN)═
CH—
, —
CCl═
CCl—
, —
C(OH)═
CH—
, —
CCl═
CH—
, —
C≡
C—
, —
CH═
N—
N═
CH—
, —
C(CH3)═
N—
N═
C(CH3)—
or —
CCl═
N—
N═
CCl—
, Z2 denotes —
(CH2)r—
or —
CH2—
C6H4—
CH2—
, r=1-10, C−
is selected from the group consisting of bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N−
), bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N−
) and tris(trifluoromethylsulfonyl)methide ((CF3SO2)3C−
), and D−
is selected from the group consisting of halogen anion, ClO4−
, BF4−
, PF6−
, AsF6−
, SbF6−
, CH3COO−
, and CH3(C6H4)SO3−
, trifluoromethylsulfonate (CF3SO3−
), bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N−
), bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N−
) and tris(trifluoromethylsulfonyl)methide ((CF3SO2)3C−
), wherein bonding to the bridge member bridge1 or bridge2 is effected via one of the radicals R17-R36, and the radicals mentioned then represent a direct bond,and wherein An1 and An2 independently represent radicals having the structural formula;
or having the structural formula or having the structural formula or having the structural formula or having the structural formula or having the structural formula or having the structural formula or having the structural formula or having the structural formula or having the structural formula or having the structural formula or wherein An1 or An2 independently represent a metal salt comprising titanium (III), vanadium (III), vanadium (IV), iron (II), cobalt (II), copper (I), silver (I), indium (I), tin (II), antimony (III), bismuth (III), cerium (III), samarium (II), dysprosium (II), ytterbium (II), or europium (II), wherein R37 to R43 independently of one another denote C1 to C18-alkyl, C2 to C12-alkenyl, C3 to C7-cycloalkyl, C7 to C15-aralkyl or C6 to C10-aryl, and R41 to R43 additionally denote hydrogen, R44 to R50 independently of one another denote hydrogen, C1 to C18-alkyl, C1 to C18-alkoxy, halogen, cyano, nitro, C1 to C18-alkoxycarbonyl or C6 to C10-aryl and R48 and R49 additionally denote an optionally benzo-fused aromatic or quasiaromatic five- or six-membered heterocyclic ring and R50 additionally independently denotes N(R51)(R52), R44 and R45 and/or R46 and R47 form a —
(CH2)3—
, —
(CH2)4—
, —
(CH2)5—
or —
CH═
CH—
CH═
CH—
bridge, Z3 denotes a direct bond or a —
CH═
CH—
or —
N═
N—
bridge, =Z4=denotes a direct double bond or a ═
CH—
CH═
or ═
N—
N═
bridge, E3 and E4 independently of one another denote O, S, NR51, C(R51)(R52), C═
O or SO2, E5 to E8 independently of one another denote S, Se or NR51, R51 and R52 independently of one another denote C1 to C12-alkyl, C2 to C8-alkenyl, C3 to C7-cycloalkyl, C7 to C15-aralkyl or C6 to C10-aryl, R53 to R60 independently of one another denote hydrogen, C1- to C6-alkyl, C1 to C18-alkoxy, cyano, C1 to C18-alkoxycarbonyl or C6 to C10-aryl, or R53 and R54 and R59 and R60 independently of one another together form a —
(CH2)3—
, —
(CH2)4—
or —
CH═
CH—
CH═
CH—
bridge, v=0-10, wherein bonding to the bridge member Bridge1 or Bridge2 is effected by one of the radicals R37-R54, or R60 and the radicals mentioned then represent a direct bond, and Bridge1 or Bridge2 independently represents a bridge member of the formula —
(CH2)n—
or —
(Y1)s(CH2)m—
(Y2)o—
(CH2)p—
(Y3)q—
, each of which is optionally substituted by C1 to C18-alkoxy, halogen or phenyl, Y1 to Y3 independently of one another independently represent O, S, NR61, COO, CONH, NHCONH, cyclopentanediyl, cyclohexanediyl, phenylene or naphthylene, beta-dicarbonyls, R61 denotes C1 to C6-alkyl, C2 to C6-alkenyl, C4 to C7-cycloalkyl, C7 to C15-aralkyl or C6- to C10-aryl, n=0-12, m=0-8, p=0-12, o=0-6, q=0-1, and s=0-1.
- is selected from the group consisting of trifluoromethylsulfonate (CF3SO3−
-
22. A compound having the structure the formula, wherein said bifunctional redox dye comprises a compound having the formula
[Cat1][M]wherein M represents a metal salt comprising titanium (III), vanadium (III), vanadium (IV), iron (II), cobalt (II), copper (I), silver (I), indium (I), tin (II), antimony (III), bismuth (III), cerium (III), samarium (II), dysprosium (II), ytterbium (II), or europium (II); -
wherein Cat1 represents a ligand having the structural formula or having the structural formula or having the structural formula or having the structural formula or having the structural formula or having the structural formula or having the structural formula or having the structural formula wherein R17 and R18 independently of one another denote C1 to C18-alkyl, C2 to C12-alkenyl, C3 to C7-cycloalkyl, C7 to C15-aralkyl or C6 to C10-aryl or R17 and R18 together form a —
(CH2)2—
, —
(CH2)3—
, or —
CH═
CH—
, R19, R20 and R22 to R25 independently of one another denote hydrogen, C1 to C18-alkyl, C1 to C18-alkoxy, halogen, cyano, nitro or C1 to C18-alkoxycarbonyl or R22 and R23 and/or R24 and R25 form a —
CH═
CH—
CH═
CH—
bridge;
R26, R27, R28 and R29 independently of one another denote hydrogen or, in pairs, a —
(CH2)2—
, —
(CH2)3—
or —
CH═
CH—
bridge, E3 and E4 independently of one another denote O, N—
CN, C(CN)2 or N—
C6- to C10-aryl, R34 and R35 independently denote hydrogen, C1 to C18-alkyl, C1 to C18-alkoxy, halogen, cyano, nitro, C1 to C18-alkoxycarbonyl or C6 to C10-aryl, R30 to R33 independently of one another denote hydrogen or C1-C6-alkyl, or R30 and R26 and/or R31 and R27 form a —
CH═
CH—
CH═
CH—
bridge, E1 and E2 independently of one another denote O, S, NR36 or C(R36)2 or E1 and E2 together form a —
N—
(CH2)2—
N—
bridge, R36 denotes C1 to C18-alkyl, C2 to C12-alkenyl, C4 to C7-cycloalkyl, C7 to C15-aralkyl or C6 to C10-aryl, Z1 denotes a direct bond, —
CH═
CH—
, —
C(CH3)═
CH—
, —
C(CN)═
CH—
, —
CCl═
CCl—
, —
C(OH)═
CH—
, —
CCl═
CH—
, —
C≡
C—
, —
CH═
N—
N═
CH—
, —
C(CH3)═
N—
N═
C(CH3)—
or —
CCl═
N—
N═
CCl—
, Z2 denotes —
(CH2)r—
or —
CH2—
C6H4—
CH2—
, r=1-10, C−
is selected from the group consisting of bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N−
), bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N−
) and tris(trifluoromethylsulfonyl)methide ((CF3SO2)3C−
), and D−
is selected from the group consisting of halogen anion, ClO4−
, BF431 , PF6−
, AsF6−
, SbF6−
, CH3COO−
, and CH3(C6H4)SO3−
, trifluoromethylsulfonate (CF3SO3−
), bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N−
), bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N−
) and tris(trifluoromethylsulfonyl)methide ((CF3SO2)3C−
).
-
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23. A method for filling an empty electrooptic device with fluid comprising warm ionic liquid electrolyte solution, the device having relatively closely spaced plates, each plate having an inwardly facing conductive surface, the plates being sealed around their periphery by a seal that encloses an area of each plate, comprising:
-
(a) introducing a small opening into the seal of an empty device;
(b) placing the empty device into a chamber along with a container of fluid comprising ionic liquid electrolyte solution;
(c) evacuating the chamber;
(d) lowering the empty device into the fluid such that the opening in the seal is located under the surface of the fluid;
(e) warming at least a portion of the fluid to a temperature of at least 40°
C.;
(f) exposing the fluid to a gas pressure greater than the pressure in the empty device to send the warm fluid into the device; and
(g) sealing the gap in the peripheral seal of the device.
-
Specification