MXPA99008945A - An improved electrochromic medium capable of producing a pre-selected color - Google Patents
An improved electrochromic medium capable of producing a pre-selected colorInfo
- Publication number
- MXPA99008945A MXPA99008945A MXPA/A/1999/008945A MX9908945A MXPA99008945A MX PA99008945 A MXPA99008945 A MX PA99008945A MX 9908945 A MX9908945 A MX 9908945A MX PA99008945 A MXPA99008945 A MX PA99008945A
- Authority
- MX
- Mexico
- Prior art keywords
- dipyridinium
- dimethyl
- electrochromic
- phenyl
- dihydrophenazine
- Prior art date
Links
- 239000000463 material Substances 0.000 claims abstract description 135
- 239000011263 electroactive material Substances 0.000 claims abstract description 86
- 239000010405 anode material Substances 0.000 claims abstract description 58
- 239000010406 cathode material Substances 0.000 claims abstract description 57
- -1 2,6-dimethylphenyl Chemical group 0.000 claims description 152
- 239000000243 solution Substances 0.000 claims description 77
- 230000003334 potential Effects 0.000 claims description 76
- 150000001875 compounds Chemical class 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- 239000000203 mixture Substances 0.000 claims description 60
- 230000002829 reduced Effects 0.000 claims description 49
- ODGCEQLVLXJUCC-UHFFFAOYSA-N tetrafluoroborate Chemical compound F[B-](F)(F)F ODGCEQLVLXJUCC-UHFFFAOYSA-N 0.000 claims description 46
- 239000011780 sodium chloride Substances 0.000 claims description 42
- LJQLCJWAZJINEB-UHFFFAOYSA-N Hexafluorophosphate Chemical compound F[P-](F)(F)(F)(F)F LJQLCJWAZJINEB-UHFFFAOYSA-N 0.000 claims description 41
- 150000003839 salts Chemical class 0.000 claims description 41
- 239000003981 vehicle Substances 0.000 claims description 33
- QDXQAOGNBCOEQX-UHFFFAOYSA-N 1-methylcyclohexa-1,4-diene Chemical compound CC1=CCC=CC1 QDXQAOGNBCOEQX-UHFFFAOYSA-N 0.000 claims description 26
- GVTGSIMRZRYNEI-UHFFFAOYSA-N 5,10-dimethylphenazine Chemical compound C1=CC=C2N(C)C3=CC=CC=C3N(C)C2=C1 GVTGSIMRZRYNEI-UHFFFAOYSA-N 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 238000010992 reflux Methods 0.000 claims description 25
- 241000894007 species Species 0.000 claims description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 23
- 150000002988 phenazines Chemical class 0.000 claims description 22
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Chemical compound C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 21
- 239000004020 conductor Substances 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- 238000007789 sealing Methods 0.000 claims description 17
- YPNMHNUVHLZMRR-UHFFFAOYSA-N 5,10-dimethyl-2,3-diphenylphenazine Chemical compound C=1C=CC=CC=1C=1C=C2N(C)C3=CC=CC=C3N(C)C2=CC=1C1=CC=CC=C1 YPNMHNUVHLZMRR-UHFFFAOYSA-N 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 12
- JVBXVOWTABLYPX-UHFFFAOYSA-L Sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 12
- 239000000975 dye Substances 0.000 claims description 12
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 12
- NTIRSDGGFHPVEV-UHFFFAOYSA-N 2,4-bis(1-methylpyridin-1-ium-4-yl)-1,3,5-triazine Chemical compound C1=C[N+](C)=CC=C1C1=NC=NC(C=2C=C[N+](C)=CC=2)=N1 NTIRSDGGFHPVEV-UHFFFAOYSA-N 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- KJCLRJLCMJCYCF-UHFFFAOYSA-N 5,10-dimethyl-2,7-diphenoxyphenazine Chemical compound C1=C2N(C)C3=CC=C(OC=4C=CC=CC=4)C=C3N(C)C2=CC=C1OC1=CC=CC=C1 KJCLRJLCMJCYCF-UHFFFAOYSA-N 0.000 claims description 10
- HDXYFMQWZDLFPV-UHFFFAOYSA-N 5,10-dimethyl-2-phenoxyphenazine Chemical compound C=1C=C2N(C)C3=CC=CC=C3N(C)C2=CC=1OC1=CC=CC=C1 HDXYFMQWZDLFPV-UHFFFAOYSA-N 0.000 claims description 10
- HEASUOPJLSCPFO-UHFFFAOYSA-N 5,10-dimethyl-2-phenylphenazine Chemical compound C=1C=C2N(C)C3=CC=CC=C3N(C)C2=CC=1C1=CC=CC=C1 HEASUOPJLSCPFO-UHFFFAOYSA-N 0.000 claims description 10
- 238000005304 joining Methods 0.000 claims description 10
- 125000003107 substituted aryl group Chemical group 0.000 claims description 10
- FJTMEJPKRKLJNO-UHFFFAOYSA-N 5,10-di(propan-2-yl)phenazine Chemical compound C1=CC=C2N(C(C)C)C3=CC=CC=C3N(C(C)C)C2=C1 FJTMEJPKRKLJNO-UHFFFAOYSA-N 0.000 claims description 9
- GLFHOJPKMOCDFC-UHFFFAOYSA-N 5,10-diethyl-2,3-dimethyl-7-(trifluoromethyl)phenazine Chemical compound CC1=C(C)C=C2N(CC)C3=CC=C(C(F)(F)F)C=C3N(CC)C2=C1 GLFHOJPKMOCDFC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- RGNYHYCNZOCXMC-UHFFFAOYSA-N 1,5,10-trimethyl-2-phenylphenazine Chemical compound C=1C=C2N(C)C3=CC=CC=C3N(C)C2=C(C)C=1C1=CC=CC=C1 RGNYHYCNZOCXMC-UHFFFAOYSA-N 0.000 claims description 8
- HUBCLUKAUZZATJ-UHFFFAOYSA-N 2-ethenyl-5,10-dimethylphenazine Chemical compound C=CC1=CC=C2N(C)C3=CC=CC=C3N(C)C2=C1 HUBCLUKAUZZATJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- RUCZRJJWYJHVFC-UHFFFAOYSA-N 2,3,7,12-tetramethyl-7H-benzo[b]phenazine Chemical compound CN1C2=CC(C)=C(C)C=C2N=C2C1=CC1=CC=CC(C)C1=C2 RUCZRJJWYJHVFC-UHFFFAOYSA-N 0.000 claims description 7
- LHUAYEMVNOTKJU-UHFFFAOYSA-N 5,10-dimethyl-2,7-diphenylphenazine Chemical compound C1=C2N(C)C3=CC=C(C=4C=CC=CC=4)C=C3N(C)C2=CC=C1C1=CC=CC=C1 LHUAYEMVNOTKJU-UHFFFAOYSA-N 0.000 claims description 7
- NNPDLECUNCWPAV-UHFFFAOYSA-N 5,10-dimethyl-5,10-dihydrobenzo[a]phenazine Chemical compound C1=CC=C2C3=NC4=CC(C)C=CC4=NC3=CC(C)C2=C1 NNPDLECUNCWPAV-UHFFFAOYSA-N 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 238000004070 electrodeposition Methods 0.000 claims description 7
- 239000003444 phase transfer catalyst Substances 0.000 claims description 7
- CJAOGUFAAWZWNI-UHFFFAOYSA-N 1-N,1-N,4-N,4-N-tetramethylbenzene-1,4-diamine Chemical compound CN(C)C1=CC=C(N(C)C)C=C1 CJAOGUFAAWZWNI-UHFFFAOYSA-N 0.000 claims description 6
- 230000002152 alkylating Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- MOIQCCJPCVEFAI-UHFFFAOYSA-N 5,10-dimethyl-2,7-bis(2-methylphenyl)phenazine Chemical compound C1=C2N(C)C3=CC=C(C=4C(=CC=CC=4)C)C=C3N(C)C2=CC=C1C1=CC=CC=C1C MOIQCCJPCVEFAI-UHFFFAOYSA-N 0.000 claims description 5
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical group [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 claims description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-M Perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000003017 thermal stabilizer Substances 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 4
- AROSEPJQYLBWHJ-UHFFFAOYSA-N 2,3,5,10-tetramethyl-7-(trifluoromethyl)phenazine Chemical compound CC1=C(C)C=C2N(C)C3=CC=C(C(F)(F)F)C=C3N(C)C2=C1 AROSEPJQYLBWHJ-UHFFFAOYSA-N 0.000 claims description 3
- 229950000688 Phenothiazine Drugs 0.000 claims description 3
- TZMSYXZUNZXBOL-UHFFFAOYSA-N Phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims description 3
- 239000003880 polar aprotic solvent Substances 0.000 claims description 3
- LHKBZFGMFKIGKJ-UHFFFAOYSA-N quinoxalino[2,3-a]phenazine Chemical class C1=CC=C2N=C3C4=NC5=CC=CC=C5N=C4C=CC3=NC2=C1 LHKBZFGMFKIGKJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 239000003638 reducing agent Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 31
- 239000001257 hydrogen Substances 0.000 claims 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 17
- 125000005605 benzo group Chemical group 0.000 claims 12
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims 12
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 10
- 125000003545 alkoxy group Chemical group 0.000 claims 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 8
- 125000003342 alkenyl group Chemical group 0.000 claims 8
- 150000002431 hydrogen Chemical class 0.000 claims 8
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims 7
- XILZQDGPCUIOCB-UHFFFAOYSA-N 2,5,10-trimethyl-3-phenylphenazine Chemical compound CC=1C=C2N(C)C3=CC=CC=C3N(C)C2=CC=1C1=CC=CC=C1 XILZQDGPCUIOCB-UHFFFAOYSA-N 0.000 claims 6
- 238000000411 transmission spectrum Methods 0.000 claims 6
- 238000000985 reflectance spectrum Methods 0.000 claims 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N Phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims 2
- 230000003078 antioxidant Effects 0.000 claims 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims 2
- 125000004344 phenylpropyl group Chemical group 0.000 claims 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 2
- 229940045714 Alkyl sulfonate alkylating agents Drugs 0.000 claims 1
- 150000001350 alkyl halides Chemical class 0.000 claims 1
- 150000008052 alkyl sulfonates Chemical class 0.000 claims 1
- 150000005323 carbonate salts Chemical class 0.000 claims 1
- 125000005842 heteroatoms Chemical group 0.000 claims 1
- 150000002391 heterocyclic compounds Chemical class 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 239000012454 non-polar solvent Substances 0.000 claims 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims 1
- 150000004897 thiazines Chemical class 0.000 claims 1
- 238000000862 absorption spectrum Methods 0.000 abstract description 32
- 239000003086 colorant Substances 0.000 abstract description 16
- 239000011521 glass Substances 0.000 description 58
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 54
- 230000015572 biosynthetic process Effects 0.000 description 47
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000007787 solid Substances 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- 238000007792 addition Methods 0.000 description 20
- 230000005540 biological transmission Effects 0.000 description 20
- INQOMBQAUSQDDS-UHFFFAOYSA-N Methyl iodide Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 19
- RUOJZAUFBMNUDX-UHFFFAOYSA-N Propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- ZNOKGRXACCSDPY-UHFFFAOYSA-N Tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 14
- 238000002835 absorbance Methods 0.000 description 13
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 125000001917 2,4-dinitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1*)[N+]([O-])=O)[N+]([O-])=O 0.000 description 11
- KTWOOEGAPBSYNW-UHFFFAOYSA-N Ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 11
- 238000005804 alkylation reaction Methods 0.000 description 9
- 230000004313 glare Effects 0.000 description 9
- 239000001187 sodium carbonate Substances 0.000 description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
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- NWAQHIWGPITNGK-UHFFFAOYSA-N 2,7-dichlorophenazine Chemical compound C1=C(Cl)C=CC2=NC3=CC(Cl)=CC=C3N=C21 NWAQHIWGPITNGK-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
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- 239000012299 nitrogen atmosphere Substances 0.000 description 8
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- 238000002390 rotary evaporation Methods 0.000 description 8
- 238000003828 vacuum filtration Methods 0.000 description 8
- NIZXKAYXSNUDOU-UHFFFAOYSA-O Ammonium hexafluorophosphate Chemical compound [NH4+].F[P-](F)(F)(F)(F)F NIZXKAYXSNUDOU-UHFFFAOYSA-O 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
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- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
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- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-Bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 5
- ZBIPZNSTXDTOAA-UHFFFAOYSA-N 5-ethyl-10-methylphenazine Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3N(C)C2=C1 ZBIPZNSTXDTOAA-UHFFFAOYSA-N 0.000 description 5
- 230000037250 Clearance Effects 0.000 description 5
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- KGJZTOFHXCFQIV-UHFFFAOYSA-N Sodium tetrafluoroborate Chemical compound [Na+].F[B-](F)(F)F KGJZTOFHXCFQIV-UHFFFAOYSA-N 0.000 description 5
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- 239000011343 solid material Substances 0.000 description 5
- LYZDGXICDJEHAD-UHFFFAOYSA-N 2-chlorophenazine Chemical compound C1=CC=CC2=NC3=CC(Cl)=CC=C3N=C21 LYZDGXICDJEHAD-UHFFFAOYSA-N 0.000 description 4
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- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
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- 239000011734 sodium Substances 0.000 description 4
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- 238000006467 substitution reaction Methods 0.000 description 4
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 4
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- RBTARNINKXHZNM-UHFFFAOYSA-K Iron(III) chloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N O-Phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M Sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N Tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001347 alkyl bromides Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
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Abstract
An improved electrochromic device, the device incorporating an electrochromic medium that comprises at least three electroactive materials having absorption spectra that add together such that the color of the electrochromic medium can be pre-selected by individually choosing the concentrations of the at least three electroactive materials. The electrochromic medium generally maintains the preselected perceived color throughout its normal range of voltages when used in an electrochromic device. The at least three electroactive materials include at least one electrochemically reducible material (cathodic material), at least one electrochemically oxidizable material (anodic material) and at least one additional electroactive material which may be either an anodic or cathodic material. Thus, there are always three electroactive materials present in the medium, with at least two either being anodic or cathodic materials. The pre-selected color may be chosen from a wide variety of colors and may be, for example, red, orange, yellow, green, blue, purple. For electrochromic mirrors for motor vehicles, a presently preferred color is gray.
Description
IMPROVED ELECTROCROMIC ENVIRONMENT CAPABLE OF PRODUCING TTN COLOR PRESELECTED
BACKGROUND OF THE INVENTION
This invention relates to an improved electrochromic medium capable of producing a preselected color and, more particularly, an improved electrochromic device having an electrochromic medium comprising at least three electroactive materials whose concentrations can be chosen to produce a preselected perceived color, in where the electrochromic medium generally maintains the preselected color perceived through its normal range of voltages when used in an electrochromic device. Electrochromic devices have been proposed for commercial applications for almost seventy years
(British Patent Specification Number 328,017 (1929) for
F. H. Smith). However, the first commercially successful electrochromic device, a darkened (which can be obscured) rear-view mirror for motor vehicles, was not introduced until 1987. Several automatic rear-view mirrors for motor vehicles have been designed which automatically change the way full reflectance (day) to the mode or modes of partial reflectance (night) for protection purposes
REF .: 31461
against the glare of the lights that emerge from the headlights of vehicles approaching from the rear. The electrochromic mirrors described in U.S. Patent No. 4,902,108 entitled "Single-Compartment, Self-Erasing, Solution-Phase Electrochromic Devices, Solutions for Use Therein, and Uses Thereof", published February 20, 1990 to H. J. Byker; Canadian Patent No. 1,300,945, entitled "Automatic Rearview Mirror System for Automotive Vehicles", published May 19, 1992 for J. H. Bechtel et al .; U.S. Patent Number 5,128,799, entitled "Variable Reflectance Motor Vehicle Mirror," published July 7, 1992 to H. J. Byker; U.S. Patent Number 5,202,787, entitled "Electro-Optic Device", published April 13, 1993 to H. J. Byker et al .; U.S. Patent No. 5,204,778, entitled "Control System for Automatic Rearview Mirrors," published April 20, 1993 to J. H. Bechtel; U.S. Patent Number 5,278,693, entitled "Tinted Solution-Phase Electrochromic Mirrors", published on January 11, 1994 for D.A. Theiste et al .; U.S. Patent Number 5,280,380, entitled "UV-Stabilized Compositions and Methods", published January 18, 1994 to H. J. Byker; U.S. Patent Number 5,282,077, entitled "Variable Reflectance Mirror," published January 25, 1994 to H. J. Byker; the
U.S. Patent Number 5,294,376, entitled "Bipyridinium Salt Solutions", published March 15, 1994 to H. J. Byker; U.S. Patent Number 5,336,448, entitled "Electrochromic Devices with Bipyridinium Salt Solutions", published August 9, 1994 to H. J. Byker; U.S. Patent Number 5,434,407, entitled "Automatic Rearview Mirror lncorporating Light Pipe", published on January 18, 1995 for F.T. Bauer et al .; U.S. Patent Number 5,448,397, entitled "Outside Automatic Rearview Mirror for Automotive Vehicles", published September 5, 1995 for. L. Tonar; and U.S. Patent No. 5,451,822, entitled "Electronic Control System", published September 19, 1995 to JH Bechtel et al., each of the patents which are assigned to the assignee of the present invention and the description thereof. each of which is incorporated herein by reference, are typical of modern automatic rear-view mirrors for motor vehicles. Such electrochromic mirrors can be used in fully integrated indoor / outdoor rear view mirror systems or as an interior or exterior mirror rearview system. In general, in the automatic rear-view mirrors of the types described in the US Patents referred to above, the interior and exterior rear-view mirrors are constituted as a medium
relatively thin electrochromic interposed and sealed between two glass elements. In most electrochromic mirrors, when the electrochromic medium which functions as a variable transmittance medium is electrically energized, it darkens and begins to absorb light, and the more light absorbs the darker electrochromic medium the mirror becomes. When the electrical voltage decreases to zero, the mirror returns to its transparent state. The electrochromic medium is contained in a sealed chamber defined by a transparent front glass element coated with a transparent conductor, a peripheral edge seal, and a rear mirror element having either a reflective layer or a transparent conductive layer in contact with the electrochromic medium that depends on whether the mirror has a third or fourth reflecting surface. The conductive layers of both the front glass element and the rear glass element are connected to electronic circuits which are effective to electrically energize the electrochromic medium to switch the mirror at night time, decreased reflectance mode when glare is detected and subsequently allows the mirror returns to the high day reflectance mode when glare persists, as described in detail in the aforementioned US patents. For purposes of clarity of the description of such structure, the front surface
of the front glass element is referred to as the first surface, and the surface within the front glass element is referred to as the second surface. The inner surface of the rear glass element is termed as the third surface and the surface behind the rear glass element is termed as the fourth surface. The electrochromic medium is typically comprised of electrochromic materials in solution phase, electrochromic materials of the electrodeposition type, electrochromic materials confined to a surface or combinations thereof. The electrochromic medium changes from a transparent condition or a high level of visible light transmission, to a highly colored state, to a moderately colored state, and to a dark state or low visible light transmission when various voltages are applied and a oxidation and electrochemical reduction. An important factor in determining the desirability of an electrochromic device is the color that is perceived when it is in the transparent state and in the dark state in any of the states between them. The perceived color of an electrochromic mirror includes the influences of the front glass element, the two transparent conductive coatings, the reflector and, what is more important, the electrochromic medium. Generally speaking, there is a desire for a gray electrochromic medium in interior mirrors and in
most of the exterior mirrors of motor vehicles because the perceived color of the reflected image closely resembles the color of the object before being reflected. Furthermore, it is desirable that the electrochromic device maintain this gray color during its darkening and lightening transitions so that the perceived colors of the reflected image do not change during these transitions. However, arguments have been presented for colored or colored mirrors. For example, commonly assigned U.S. Patent No. 5,278,693 to D. A. Theiste et al., Describe adding an electrochemically inactive and stable compound to a phase-in-solution electrochromic device to provide a blue dye. This electrochemically inactive compound is essentially a dye which is normally present at low concentrations, and will provide a dye perceived in the device only at higher states of reflectance or transmittance when little or no voltage is applied. In other applications such as architectural windows, sliding roofs, screens and specialty windows, various colors (eg blue, green, purple, yellow) as well as gray may be desirable for numerous reasons. For example, it may be desired that certain electrochromic windows are dyed to match the decoration of the room, provide an increase in
Contrast or obscure gray-scale filters for screens that emit particular light colors, or to provide a building with a particular color or appearance. One problem in the art has been the inability to preset a color of an electrochromic device and at the same time ensure that the device generally maintains the desired color when it is in the transparent state and in the dark state, and in any state between them. With such devices used as electrochromic rear-view mirrors for motor vehicles and many applications in windows, the desired color is one that is perceived as gray. For other applications, colors that are perceived other than gray (for example, red, yellow, green, blue, purple) may be desirable. Accordingly, it is desirable to provide an improved electrochromic medium having at least three electroactive materials whose concentrations can be chosen to produce a preselected perceived color, wherein the electrochromic medium generally maintains the preselected color perceived through its normal range of voltages when It is used in an electrochromic device.
OBJECTIVES OF THE INVENTION
Accordingly, a principal objective of the present invention is to provide an improved electrochromic medium having at least three electroactive materials whose relative concentrations can be chosen to produce a preselected perceived color wherein the electrochromic medium generally maintains the preselected color perceived through its normal range of voltages when used in an electrochromic device. Another object of the present invention is to provide an improved electrochromic medium having at least three electroactive materials whose concentrations can be chosen to produce a perceived gray color, wherein the electrochromic medium generally maintains the gray color through its normal range of voltages. when used in an electrochromic device. Still another objective of the present invention is to provide novel electroactive materials.
BRIEF DESCRIPTION OF THE INVENTION
The above and other additional objectives, which will become apparent from the specification in its entirety, including the drawings, are carried out
according to the present invention by providing an electrochromic device having an electrochromic medium comprising at least three electroactive materials having absorption spectra that are added together so that the color of the electrochemically activated electrochromic medium can be selected previously by individually selecting the concentrations of at least three electroactive materials. The electrochromic medium generally maintains the preselected color perceived through its normal range of voltages when used in an electrochromic device. At least three electroactive materials include at least one electrochemically reducible material (cathodic material), at least one electrochemically oxidizable material (anodic material) and at least one additional electroactive material which may be an anodic or cathodic material. Therefore, there are always at least three electroactive materials present in the medium, wherein at least two are anodic or cathodic materials. The preselected color can be chosen from a wide variety of colors and can be, for example, gray, red, orange, yellow, green, blue and purple. For electrochromic mirrors for motor vehicles and many applications in windows, the currently preferred color is gray.
BRIEF DESCRIPTION OF THE DRAWINGS
The subject matter which is considered as the invention is particularly highlighted and distinctly claimed in the conclusive portion of the specification. The invention, together with the additional objects and advantages thereof, can be better understood with reference to the following description taken in connection with the accompanying drawings, in which like numbers represent like components, in which: Figure 1 is an enlarged cross-sectional view of an electrochromic device; Figure 2 illustrates scale absorption spectra for the electrochemically activated states of the following individual electrochromic materials: 5,10-dimethyl-5,10-dihydrophenazine (Al); 2,7-diphenoxy-5,10-dimethyl-5,10-dihydrophenazine (A6); 1, 1 '-dimethyl-4, 4' - (1, 3, 5-triazine-2,4-diyl) dipyridinium (C4) diperchlorate; bis (hexafluorophosphate) of 1,1'-dimethyl-2- (3-phenyl (n-propyl) -4,4'-dipyridinium (C5), wherein each of the absorption spectra is scaled for the relative concentrations of the activated states that could be present in an activated device, as well as the composite spectrum for the activated state of an electrochromic medium that originally comprises Al to 80% and A6
to 20% of the total anodic materials, plus C4 to 50% and C5 to 50% of the total cathode materials; Figure 3 illustrates the scale absorption spectra for the electrochemically activated states of the following individual electrochromic materials: 5,10-dimethyl-5,10-dihydrophenazine (A); 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine (B); and tungsten trioxide (C), wherein each absorption spectrum is scaled with respect to the relative concentrations of the activated states that could occur in an activated device; as well as the spectrum
(D) compound which is the sum of the scale spectra of the activated states of these three electrochromic materials; Figure 4 shows several curves representing the color coordinates of various electrochromic mirrors incorporating various electrochromic means as the mirrors make a transition from the transparent or high reflectance state to the dark or low reflectance state; Figure 5 shows several curves representing the color coordinates of various electrochromic means incorporated in various electrochromic windows as the windows make a transition from their transparent or high transmission states to their dark or low transmission states; Figure 6 shows several color coordinate curves that indicate the graduation phenomenon in windows
electrochromic that incorporate various electrochromic media as the windows make a transition from their transparent or high transmission states to their dark or low transmission states; and Figure 7 is a front elevational view schematically illustrating an indoor / outdoor electrochromic rear view mirror means for motor vehicles wherein the interior and exterior mirrors incorporate the mirror assembly of the present invention.
DETAILED DESCRIPTION
Figure 1 shows a cross-sectional view of an electrochromic device 110 which can be a mirror, a window, a display device and the like. The device 110 has a front transparent element 112 having a front surface 112a and a rear surface 112b, and a rear element 114 having a front surface 114a and a rear surface 114b. Since some of the layers of the mirror are very thin, the scale will be distorted for clarity. In addition, also for purposes of clarity of the description of such structure, the following designations will be used in the following. The front surface 112a of the front glass element will be referred to as the first surface, and the rear surface
112b of the front glass element, as the second surface. The front surface 114a of the rear glass element will be referred to as the third surface, and the rear surface 114b of the glass element of the rear part will be referred to as the fourth surface. The front transparent element 112 can be any material which is transparent and has sufficient strength to allow operation under conditions, for example, of varying temperature and pressure that are commonly found in the automotive environment. The front element 112 can be constituted of any type of borosilicate glass, soda and lime glass, floating glass or any other material such as, for example, a polymer or plastic that is transparent in the visible region of the electromagnetic spectrum. The front element 112 is preferably a glass sheet with a thickness ranging from 0.5 mm to approximately 12.7 mm. The rear element 114 must satisfy the operational conditions indicated above, except that if the electrochromic device is a mirror, the rear element 114 need not be transparent, and therefore, may be constituted of polymers, metals, glass, ceramic materials and preferably It is a glass sheet with a thickness that varies from 0.5 mm to approximately 12.7 mm.
A layer of electrically conductive, transparent material 116 is deposited on the second surface 112b to act as an electrode. Conductive and transparent material 116 may be any material that: is substantially transparent to visible light; adhere well to the front element 112 and maintain this bond when the epoxy seal 118 is attached thereto; be resistant to corrosion by any material within the electrochromic device; that is resistant to corrosion by the atmosphere; and that has a minimum specular diffusion or reflectance and good electrical conductance. Conductive and transparent material 116 may be fluorinated dope tin oxide (FTO), tin doped indium oxide (ITO), ITO / metal / lTO (IMI) as described in "Transparent Conductive Multilayer-Systems for FPD Applications" , by J. Stollenwerk, B. Ocker, KH Kretschmer of LEYBOLD AG, Alzenau, Germany, and the materials described in U.S. Patent No. 5,202,787 mentioned above, such as TEC 20 or TEC 15, available from Libbey Owens -Ford Co. (LOF) of Toledo, OH. The co-filed United States Patent Application entitled "AN IMPROVED ELECTRO-OPTIC DEVICE INCLUDING A LOW SHEET RESISTANCE, HIGH TRANSMISSION TRANSPARENT ELECTRODE" discloses a transparent scraping-resistant, high-transmission, low-resistance blade electrode forming strong bonds with adhesives, which is not sensitive to oxygen and can be bent
to form a convex or spherical electro-optical mirror element or it can be tempered in air without adverse side effects. The description of these commonly assigned applications are incorporated herein by reference. Similar requirements are needed for the layer 120 deposited on the third surface 114a, whether they constitute a transparent conductive material used in electrochromic windows and in mirrors having a fourth reflecting surface, or a combined reflector / electrode (discussed below) used in mirrors. electrochromic that have a third surface reflector. The conductance of the layer or layers of the transparent conductive material (116 and / or 120) will depend on its thickness and composition. As a general rule, TEC coatings from LOF are a more neutral color than simple FTO and ITO coatings. This difference in color impacts the neutrality of the total color of the reflected image when the mirror is completely obscured because most of the reflection observed by the driver comes from the first and second surfaces. Therefore, if transparent conductive material exists on the second surface of the mirror that is not neutral in color, it may impact the color of the reflected image observed by the driver. In certain automotive mirror systems it is beneficial to use TEC coatings as the transparent conductor in the mirror
interior, but not greater in the exterior mirrors. When thin glass is used for larger TEC exterior mirrors which can not be used because the coatings are applied over the waterline, and it is very difficult to manufacture this thin glass in large waterlines and even more difficult to apply coatings while thin glasses are manufactured on a waterline. Therefore, thin glass coated on a waterline is currently not commercially available. If a simple ITO coating is used on the outer mirror, then the reflected image will not be neutral when the mirror is in its completely darkened state and one will notice a difference in color between the reflected images of this outer mirror and the mirrors. interiors made with TEC glass coatings. The United States patent application entitled "A ELECTROCHROMIC MIRROR WITH TWO THIN GLASS ELEMENTS AND A GELLED ELECTROMROMIC MÉDIUM" describes a transparent conductive coating of preferred neutral color that can be used on the second surface of a mirror or a window and that will eliminate the problem described. The entire description of this copending commonly assigned U.S. patent application is incorporated herein by reference. This transparent conductive coating of neutral color provides a particularly advantageous combination with the medium
gray electrochromic of the present invention. The combination of a bright almost achromatic reflector, a gray electrochromic medium and a transparent conductor coating of neutral color provides, for the first time, a rearview mirror which is perceived as neutral gray throughout its entire reflectance range, including intermediate reflectances. For electrochromic mirrors, the reflector can be placed on the fourth surface, in which case a transparent conductive electrode layer is deposited on the third surface 114a, or the reflector can be placed on the third surface 114a according to the description of the application for a United States Patent entitled "ELECTROCHROMIC REARVIEW MIRROR INCORPORATING TO THIRD SURFACE METAL REFLECTOR" filed on or about April 2, 1997, the entire description of this copending, commonly assigned United States patent application is incorporated in the present as a reference. In this case, the third reflecting surface is duplicated as an electrode and the transparent conductive layer on the third surface is not necessary. A heater (not shown) can be placed directly on the fourth surface 114b. The coating 120 of the third surface 114a (either a transparent conductor or a reflector / electrode) is sealingly joined to the coating 116 on the second
surface 112b near the outer perimeter by a sealing member 118, whereby a chamber 122 is defined. For electrochromic mirrors, the sealing member 118 preferably contains glass spheres (not shown) that hold the elements 112 and 114 transparent in a parallel and separate relationship. The sealing member 118 can be any material which is capable of adhesively bonding the coatings of the second surface 112b to the coatings of the third surface 114a to seal the perimeter so that the electrochromic means 124 does not leak from the chamber 122. Optionally, the transparent conductive coating layer 116 and the layer of the third surface 120
(transparent conductive material or reflector / electrode) can be removed over a portion where the sealing member 118 is placed (not in the entire portion, which otherwise activates the potential which can not be applied to the two coatings ). In such a case, the sealing member 118 should bond the glass well. The performance requirements for a perimeter seal member 118 used in an electrochromic device are similar to those of a perimeter seal used in a liquid crystal device (LCD) which are well known in the art. The seal must have good adhesion to glass, metals and metal oxides, must have low permeabilities for oxygen, moisture vapor and others
vapors and harmful gases, and must not interact with, or contaminate the electrochromic or liquid crystal material which means that it contains and protects it. The perimeter seal may be applied by means commonly used in the LCD industry such as by screen printing or dispersion. Fully airtight seals such as those made with glass frit or glass solder can be used, but the high temperatures involved in the processing (usually close to 450 ° C) of this type of seal can cause numerous problems such as warpage of the substrate. glass, changes in the properties of the transparent conductive electrode and oxidation or degradation of the reflector. Due to their low processing temperatures, organic sealing resins with lower processing temperatures, thermoplastic, thermosetting or UV curing are preferred. Such organic resin sealing systems for LCD are described in U.S. Patent Nos. 4,297,401, 4,418,102, 4,695,490, 5, 596, 023 and 5, 596, 024. Due to their excellent adhesion to glass, low oxygen permeability and good solvent resistance, organic sealing resins based on epoxy material are preferred. These epoxy resin seals can be cured by UV radiation, such as described in U.S. Patent No. 4,297,401, or they can be thermally cured, for example with mixtures of liquid epoxy resin with liquid polyamide resin or
dicyandiamide, or they can be homopolymerized. The epoxy resin may contain fillers or thickeners to reduce flow and shrinkage for example fumed silica, silica, mica, clay, calcium carbonate, alumina, etc., and / or pigments to add color. Pretreatment fillers with hydrophobic or xylan surface treatment are preferred. The crosslink density of the cured resin can be controlled by using mixtures of monofunctional, bifunctional and multifunctional epoxy resins, and curing agents. Additives such as xylanes or titanates can be used to improve the hydrolytic stability of the seal, and spacers such as glass spheres or rods can be used to control the final seal thickness and the separation of the substrate. Epoxy resins suitable for use in a perimeter seal member 118 include, but are not limited to: "EPON RESIN" 813, 825, 826, 828, 830, 834, 862, 1001F, 1002F, 2012, DPS-155, 164, 1031, 1074, 58005, 58006-, 58034, 58901, 871, 872 and DPL-862 available from Shell Chemical Co., Houston, Texas; "ARALITE" GY 6010, GY 6020, CY 9579, GT 7071, XU 248, EPN 1139, EPN 1138, PY 307, ECN 1235, ECN 1273, ECN 1280, MT 0163, MY 720, MY 0500, MY 0510 and PT 810 available from Ciba Geigy, Hawthome, NY; "D.E.R-" 331, 317, 361, 383, 661, 662, 667, 732, 736, "D.E.N." 431, 438, 439 and 444 available from Dow Chemical Co., Midland, Michigan. The suitable epoxy curing agents
include polyamides V-15, V-25 and V-40 from Shell Chemical Co.; "AJICURE" PN-23, PN-34 and VDH available from Aj inomoto Co. , Tokyo Japan; "CUREZOL" AMZ, 2MZ, 2E4MZ, C1IZ, C17Z, 2PZ, 2IZ and 2P4MZ available from Shikoku Fine Chemicals, Tokyo, Japan; "ERISYS" DDA or DDA accelerated with U-405, 24EMI, U-410 and U-415 available from CVC Specialty Chemicals, Maple Shade, NJ.; "AMICURE" PACM, 352, CG, CG-325 and CG-1200 available from Air Products, Allentown, PA. Suitable fillers include fumed silica such as "CAB-O-SIL" L-90, LM-130, LM-5, PTG, M-5, MS-7, MS-55, TS-720, HS-5 , -EH-5 available from Cabot Corporation, Tuscola, IL; "AEROSIL" R972, R974, R805, R812, R812 S, R202, US204 and US206 available from Degussa, Akron, OH. Suitable clay fillers include BUCK, CATALPO, ASP NC, SATINTONE 5, SATINTONE SP-33, TRANSLINK 37, TRANSLINK 77, TRANSLINK 445, TRANSLINK 555 available from Engelhard Corporation, Edison, NJ. Suitable silicate fill materials are SILCRON G-130, G-300, G-100-T and G-100 available from SCM Chemicals, Baltimore, NM. Suitable xylan coupling agents for improving the hydrolytic stability of the seal are Z-6020, Z-6030, Z-6032, Z-6040, Z-6075 and Z-6076 available from Dow Corning Corporation, Midland, MI. Suitable precision glass microsphere separators are available in a variety of sizes from Duke Scientific, Palo Alto, CA.
When discussing colors it is useful to refer to the Commission Internationale de I 'Eclairage' s (CIÉ) 1976 CIELAB Chromaticiti Diagram (commonly referred to as the L * a * b * diagram). Color technology is relatively complex, but a very broad discussion is provided by FW Billmeyer and M. Saltzman in Principies of Color Technoloav, second edition, J. Wiley and Sons Inc. (1981) and the present description, to the extent that which is related to the technology and terminology of colors, generally follows that discussion. In the diagram L * a * b *, the asterisk defines luminance, a * denotes the red / green value and b * indicates the yellow / blue value. Each of the electrochromic media has absorption spectra at each particular voltage that can be converted to a designation of three numbers, their values L * a * b *. To calculate a set of color coordinates, such as the L * a * b * values from the transmission or spectral reflectance, two additional paragraphs are required. One is the spectral power division of the source or illuminant. The present description uses standard Illuminant A CI to stimulate light from a car's front lamps and uses the standard CIEC Illuminant D65 for similar daylight. The second necessary indent is the spectral response of the observer. The present description uses the standard observer CIÉ of 2 °. The illuminant / observer combination that is generally used for mirrors
then it is represented as grade A / 2 and the combination used generally for windows is represented as D65 / 2 °. According to the present invention, the electrochromic device includes an electrochromic medium comprising at least three electroactive materials having absorption spectra when they are electrochemically activated which are added together so that the color of the electrochromic medium can be preselected by individually choosing the concentrations of at least three electroactive materials. The at least three electroactive materials include at least one material that can be reduced (cathodic material), at least one oxidizable material
(anodic material) and at least one additional electroactive material which may be an anodic or cathodic material. Therefore, there are always three electroactive materials present in the medium, with at least two constituting anodic or cathodic materials. Generally, all three electroactive materials are electrochromic so that a change in absorption coefficient occurs in at least one wavelength in the visible spectrum when activated electrochemically. However, there are cases in which it is desirable to have at least two electrochromic anodic materials combined with at least one generally colorless electroactive cathodic material or,
alternatively, at least two electrochromic cathode materials combined with at least one generally colorless electroactive anodic material. In any case, at least two of the electroactive materials must be electrochromic. Finally, at least three of the electroactive compounds in their equilibrium states with zero potential, not activated in solution are not ionic, and their electrochromic medium also includes an electrolyte, although it should be understood that the additional electrolyte can be included when one or more than the electroactive compounds is ionic. The electrochromic medium includes electroactive cathode and anodic materials that can be independently chosen from at least the following three categories: (i) Phase in Solution - A material contained in ionically conductive electrolyte solution which remains in solution in the electrolyte when reduced u oxidizes electrochemically. The electroactive materials in continuous solution phase of a free lift gel according to the teachings of the United States patent application serial number 08 / 616,967 entitled "IMPROVED ELECTROCHROMIC LAYER AND DEVICES COMPRISING SAME";
(ii) Surface confined - a material directly attached to an electronically conducting or confined electrode in close proximity to it which remains attached or confined when reduced or electrochemically oxidized; and (iii) Electrodeposition - a material contained in solution in the ionically conductive electrolyte which forms a layer on the electronically conductive electrode when it is electrochemically reduced or oxidized. In addition, the electrochromic medium can also include other materials such as solvents, light absorbing substances, light stabilizers, thermal stabilizers, antioxidants, thickeners or viscosity modifiers and a free support gel (which includes a polymeric matrix). The absorption spectra of electrochromic materials when activated electrochemically must be added together so that the color of the electrochromic medium can be preselected by individually choosing the concentrations of the layer thicknesses of the electrochromic materials. In a stable device, each electron that is removed by oxidation of an anode material must be balanced by an electron that is accepted by reduction of a cathodic material. Therefore, in a medium
electrochromic that contains three or more electroactive materials, the total number of anodic species that are oxidized must be equal to the total number of cathodetic species that are reduced. This limitation is an important aspect to ensure the ability to produce a preselected color according to the present invention. To illustrate this point, it is well known that blue can be added to yellow to generate green, however, if anodic material with a change from colorless to dark blue when oxidized, and a cathode material with a change from colorless to light yellow when reduced, they are added together, they will always produce an electrochromic medium with the same tone throughout their normal voltage range regardless of the proportions of anodic and cathodic material concentrations. This is because the total amount of oxidized anodic material must be equal to the total amount of reduced cathodic material. Therefore, even if the amount of cathodic material that turns yellow when reduced is doubled or even tripled, the color will be the same because, for each cathodic species that turns yellow, an anodic species will turn blue. However, in order that the concentration of both the cathodic electroactive materials and the anodic electroactive materials are limited in current in systems in phase in solution, the total concentration of one type may be different from the total concentration of the other type
due to differences in the diffusion coefficients in the electrochromic medium. Often the material or materials with smaller diffusion coefficients are present at slightly higher concentrations. In order that an electrochromic medium containing anodic and cathodic electroactive multiple materials be able to generate a preselected color, and generally maintain the preselected color perceived during the darkening and lightening transitions, and simultaneously is desirable for commercial applications, the medium must be stable photochemically and thermally, and all anodic materials present in the electrochromic medium must have redox potentials similar to each other and all the cathode materials present in the electrochromic medium must have similar redox potentials. If the perceived color of the device is to be consistent during the operation of the electrochromic device (ie, at various voltages applied and during the coloration and clearance transitions) the redox potentials of all electrochemically activated cathode materials during normal operation should be similar to each other, preferably within 60 mV each other, and the redox potentials of all of the electrochemically activated materials during the operation should be
similar to each other, preferably within 60 mV each other. More preferably, the redox potentials of all the cathode materials must be within 40 mV of each other and the redox potentials of all the anodic materials must be within 40 mV of each other. Even if the redox potentials of the cathodic materials that contribute color are not similar to each other, or the redox potentials of the anodic materials that contribute to color are not similar to each other, a device containing such an electrochromic medium can still show a single color due to the combination of all the colors of the cathode materials or all the colors of the anodic materials at an applied voltage high enough to reduce all the cathode materials that reach the cathode and oxidize all the anodic materials that reach the anode. However, at lower applied voltages or during color transitions or especially during clearance transitions, the colors due to the more easily reduced cathodic material, ie, those with the highest redox potentials and / or anodic materials that are more easily oxidized , that is, those with the lowest redox potentials will dominate the perceived color of the electrochromic medium. This phenomenon is commonly referred to as graduation. If the redox potentials are similar to each other (and assuming the kinetics of the electrode reactions the
which are at least somewhat similar and the electrochromic materials have a color which only varies in the chroma perceived through the voltage range of the device) then the color due to the electrochromic medium will be a composite consisting of all of the cathode materials and Anodic that contribute color through the operation of the device at various voltages applied and during the transitions of coloration and clearance. In other words, the absorption spectra of the individual cathode materials will be added together and the absorption spectra of the individual anodic materials will be added together, so that the absorption spectra resulting from the electrochromic medium will produce a consistent perceived color or tone to through the operation of the device. The electrochromic devices should preferably be photochemically stable. Devices used in applications such as rear-view mirrors, especially on the outside of motor vehicles, must have a means that prevents harmful photons from reaching the electrochromic medium or must have an electrochromic medium that is stable with respect to photochemical degradation, so less for exposure to sunlight during the useful life of the device while the device is in a nominally transparent state. For electrochromic devices
used in applications such as motor vehicles or architectural windows or glass placement, the device must prevent harmful photons from reaching the electrochromic medium or must have an electrochromic medium that is stable with respect to photochemical degradation both in a nominally transparent state and during the electrochemical activation. For electrochromic devices and media which contain multiple cathodic electrochromic materials and / or multiple anodic electrochromic materials, it should be avoided that photons harmful to any of the electrochromic materials reach that material, or that each material and a medium as a whole be stable with with respect to photochemical degradation. Finally, the electrochromic medium should preferably be thermally stable or should be such a medium that it does not lose its ability to color or permanently discolor due to thermal degradation. Many electrochromic means proposed in the art suffer from the lack of thermal stability for one or more electrochromic materials in their nominally transparent oxidation states or especially in their colored oxidation states. The lack of thermal stability results in a poor cycle time for the electrochromic device. In electrochromic media containing multiple multiple and / or anodic cathodic materials, each electrochromic material
must be thermally stable enough in each of its oxidation states present in the device, with or without applied voltage, to provide the device with thermal stability suitable for its intended use and duration, or the thermal degradation of these materials should not Remove the color of the device or prevent proper operation of the device. As stated in the foregoing, the electrochromic means of the present invention comprises at least three electroactive materials having absorption spectra in their activated state which are summed together so that a preselected color of the electrospheric medium can be made by individually choosing the concentrations, relative concentrations or layer thickness of at least three electroactive materials contained in the medium. This pre-selected color can be a wide range of perceived colors, such as red, orange, yellow, green, blue, gray, etc. Tables 1 to 9 mention various cathodic electrochromic materials and various anodic electrochromic materials which, when dissolved in the appropriate solvent or solvent systems, including enough dissolved electrolyte to provide ionic conductivity to the solution, can be used as phase-dependent electrochromic materials. solution. The solvents used are usually organic solvents
polar aprotic described in U.S. Patent Number 4,902,108. Many of these solvents, the materials in Tables 1 to 9 show two chemically reversible waves in a cyclic voltammogram run to an inert electrode at room temperature. The first wave of cyclic voltammogram is usually due to an electron by molecule reduction or an electron by oxidation of molecule which is accompanied by a change from colorless to slightly colored until significantly colored (eg absorbs light at least one length wave in the visible spectrum). The use of these materials in electrochromic devices is normally restricted to the electrochemical activation of the materials to this reduced state of an electron or oxidized state of an electron. These reduced states for cathode materials or oxidized states for anodic materials have a particular light absorption spectrum that generally follows Beer's law through its range of concentrations in activated electrochromic devices, with the exception of some materials which at higher concentrations Elevations of the reduced state show complication in the spectrum due to what is considered to be a dimerization. To the extent that the voltage applied to an electrochromic device containing these materials is restricted to the normal range in which only a reduced state of an electron or an oxidized state of an electron is
produced on the electrodes, the materials will make a consistent color contribution that varies only in the amount of absorption. If the voltage is too great, the color or the visible light absorption spectrum of the state or states reduced twice and / or state or oxidized states will twice contribute to the total spectrum of the electrochromic medium and therefore to the electrochromic device. Moving out of the normal voltage range will often result in a perceived color change of the medium. For several of the materials in Tables 1 and 2, the difference in redox potential for the first reduction of an electron and the second reduction of an electron is usually very small and therefore the normal voltage range for a device containing These materials is very limited. Generally, if an electrochromic medium contains both anodic and cathodic electrochromic materials from tables 9, then the normal voltage across the medium is from about 0.3 volts less than the difference in redox potentials between the cathodic materials and anodic materials to approximately 0.2 to 0.4 volts more than the difference in these redox potentials. The redox potentials in Tables 1 to 9 are determined by differential pulse voltammetry at a platinum working electrode in an argon purged propylene carbonate solution containing 0.2 molar tetrafluoroborate
of tetraethylammonium with an internal reference compound of known redox potential. Finally, all the redox potentials in Tables 1 to 9 are given in relation to the redox potential of 5,10-dimethyl-5,10-dihydrophenazine which is set at 0.300 volts. Tables 1 to 4 include four groups of cathode electrochromic materials which change from colorless to lightly colored until significantly colored when reduced electrochemically. The tables also provide the redox potentials for the first electron reduction of each material and the maximum absorbance wavelengths and the logarithms of the absorption coefficients at these wavelengths for the reduced state of an electron or almost the entire of the included cathode materials. Tables 5 and 6 list two additional groups of cathode electrochromic materials and the redox potentials for the first one electron reduction for each material. The redox potential for electrochemical reduction is similar within each table or group. All of the cathode materials in Table 1 have their redox potentials between -0.112 volts and -0.132 volts, however, the reduced electron materials have different absorption spectra with different wavelengths of maximum absorbance, which results in different perceived colors, when the materials
reduced. For example, in table 1, materials 1 and 4 appear green when they are reduced and materials 2 and 5 appear blue when they are reduced. By choosing various relative concentrations of, for example, materials 1 and 2, the contribution of the cathode materials to the color of the electrochromic medium can vary between blue, blue-green and green. All of the cathode materials in Table 2 have their redox potentials between -0.192 volts and -0.216 volts. However, the spectral absorbances of the materials in their reduced states show that the materials appear different in color from each other and can be combined in various relative concentrations to impart a particular color contribution (different from any of the materials individually) to a medium electrochromic that contains this combination of cathodic material. All of the cathode materials in Table 3 have their redox potentials between -0.276 volts and -0.304 volts, however, there are differences in their absorption spectra that lead to useful combinations of these cathode materials in electrochromic devices. The cathode materials in Table 4 have similar redox potentials and are between -0.340 volts and -0.376 volts. Although materials 1, 3 and 5 have at least somewhat similar spectra and similar blue appearance in their
reduced states, materials 2 and 4 have spectra and appearance of color significantly different. When it is reduced, material 2 appears purple and material 4 appears gray. This allows particularly advantageous combinations of materials in Table 4 especially with respect to obtaining a gray color in a mirror or electrochromic window. The cathode materials in Table 5 have redox potentials between -0.424 and -0.436. Although the absorption coefficients have not been measured, the compounds have different absorption spectra when they are electrochemically reduced and can be combined with each other and / or with anodic materials to provide useful color contributions to the appearance of electrochromic devices. The cathode materials in table 6 have redox potentials between -0.472 and -0.492. Although the absorption coefficients have not been measured, the compounds have different absorption spectra when reduced electrochemically and can be combined with each other and / or with anodic materials to provide useful color contributions for the appearance of electrochromic devices.
TABLE 1
E 1/2 Radical Cationic? max (log e)
1. bis (tetrafluoroborate) of l, r-diphenyl-4,4'-dipyridinium -0.100 434 (4.57) 644 (4.31) 710 (4.22) 2. bis (tetrafluoroborate) of l, -bis (2,6-dimethylphenyl) - 4,4'-dipyridinium -0.112 400 (4.64) 600 (4.30) 712 (3.84) 3. bis (tetrafluoroborate) of l, r-bis (3,5-dimethylphenyl) -4,4'-dipyridinium -0.116 428 ( 4.54) 572 (4.20) 642 (4.08) 710 (3.91)
4. bis (hexafluorophosphate) of l-phenyl- - (4-dodecylphenyl) -4,4'-dipyridinium -0.116 436 (4.50) 6.08 (4.18) 644 (4.23) 710 (4.13)?
. bis (tetrafluoroborate) of l, -bis (trimethylphenyl) -4,4'-dipyridinium -0.116 400 (4.63) 600 (4.33) 712 (3.86) 6. bis (hexafluorophosphate) of l- (4-cyanophenyl) -methyl -4.4'-dipyridinium -0.132
TABLE 2
E 1/2 Radical Cationic? max (log e)
1. bis (hexafluorophosphate) of l- (3,5-dimethoxyphenyl) -methyl-4,4'-dipyridinium -0.192 410 (3.75) 606 (4.16) 710 (3.75) 2. bis (hexafluorophosphate) of l-methyl- - phenyl-4,4'-dipyridinium -0.204 414 (4.36) 608 (3.87) 712 (3.45) 3. bis (hexafluorophosphate) of l-methyl- - (2-methylphenyl) -4,4'-dipyridinium -0.216 398 ( 4.55) 602 (4.21) 718 (3.62) to
4. bis (hexafluorophosphate) of l- (4-methoxyphenyl) -l'-methyl-4,4'-dipyridinium -0.216 428 (4.35) 610 (4.20) 720 (3.74) 00
. bis (hexafluorophosphate) of l-methyl- - (2,4,6-trimethylphenyl) -4,4'-dipyridinium -0.216 398 (4.56) 602 (4.19) 722 (3.55)
TABLE 3
E 1/2 Radical Cationic? max (log e)
1. bis (tetrafluoroborate) of 1, 2,6-trimethyl-phenyl-4,4'-dipyridinium -0.276 410 (4.35) 604 (4.14) 2. bis (tetrafluoroborate) of 1, -dimethyl-2,6-diphenyl- 4,4'-dipyridinium -0.292 400 (4.47) 636 (4.19) 3. bis (tetrafluoroborate) of l, r-bis (3-phenyl (n-propyl)) - 4,4'-dipyridinium -0.296 398 (4 , 61) 604 (4.16) 732 (3.50) 4. bis (tetrafluoroborate) of 1, r-dimethyl-4,4'-dipyridinium -0.304 394 (4.56) 604 (4.12) 738 (3.50 00
TABLE 4
E 1/2 Radical Cationic? max (log e)
1. bis (hexafluorophosphate) of l, -dimethyl-2- (3-phenyl (n-propyl)) - 4,4'-dipyridinium -0.340 396 (4.57) 608 (4.18) 730 (3.47) 2. diperchlorate of l, - dimethyl-4,4 '- (1, 3,5-triazine-2,4-diyl) dipyridinium -0.352 556 (3.86) 3.bis (tetrafluoroborate) of l, -dibenzyl-2,2', 6,6 ' -tetramethyl-4,4"-dipyridinium-0,360 396 (4.49) 590 (4.22) 688 (3.83) 4. bisfiexafluorophosphate) of l, r-ethylene-, 4'-dimethyl-2,2'-dipyridinium * -0.360 432 (3.81) 468 (3.85) 748 (3.53) or
. bis (tetrafluoroborate) of l, -dimetiI-2,2'-bis (3-phenyl (n-propyl)) - 4,4'-dipyridinium -0.376 396 (4.60) 610 (4.25) 725 (3.61)
* IUPAC name: bis (hexafluorophosphate) of 6,7-dihydrodipyrido- [1, 2-a: -c] pyrazinadiimio
m
TABLE 5
E 1/2
1. 1, 6-diethyl-l, 6-diazapyrene-2,5,7,10-tetracetone-0.424 2. bis (tetrafluoroborate) of 1, 1 ', 2, 2', 3, 3 ', 4,4'- Octahydro-8,8'-biquinoizinium-0.436 3.bis (tetrafluoroborate) of 1, 1 ', 2-trimethyl-2', 6,6, -tri (2-phenylethyl) -4,4, -dipyridinium- 0.436
i
TABLE 6
^ 1/2 1. 2,6-dimethylbenzoquinone -0.472 2. 1, 4-dihydroxyanthraquinone -0.472 3. l-Methyl-4- (l, 3,5-triazine-2-yl) pyridinium hexafluorophosphate -0.472 4. bis (hexafluorophosphate) of 1, 2,2 ', 6-pentamethyl-6'-n-hexyl-4,4'-dipyridinium-0,484 5. bis (hexafluorophosphate) of 1, 2,2'-tetramethyl-6 , 6'-bis-n-hexyl-4,4'-dipyridinium -0.488 1
6. bis (hexafluorophosphate) of 1, 2,2 ', 6-pentamethyl-6' - (3-phenyl (n-propyl)) - dipyridinium -0.492 t
Tables 7 to 9 include groups of anodic materials that are colorless or slightly colored which change to significantly colored when oxidized electrochemically. The tables also provide the redox materials for the first oxidation of an electron of each material and the wavelengths of the maximum absorbance and the logarithms of the absorption coefficients at these wavelengths for the oxidized state of an electron of the anodic materials included All the anodic materials in table 7 have their redox potentials between 0.256 volts and 0.264 volts, however, the oxidized materials of an electron have all different absorption spectra. The oxidized materials appear blue, brown, purple or green and can be combined in selected relative concentrations in electrochromic devices to impart any of numerous particular or predetermined color contributions. The totality of the anodic materials in table 8 have their redox potentials between 0.290 volts and 0.308 volts. The wavelength of the maximum absorbance for the peak absorbance of the oxidized state of these materials varies from 460 nanometers to 532 nanometers. Many useful combinations of these materials can be used at selected relative concentrations in devices
electrochromic to obtain a contribution of particular color appearance. Finally, all the anodic materials in table 9 have a similar redox potential and are between 0.344 volts and 0.352 volts. Although the redox potentials are similar, the appearance of color and the color spectra are different and the combinations at selected relative concentrations are useful in imparting a particular color appearance to the electrochromic devices.
TABLE 7
E 1/2 Cationic Radical
? max (log e)
1. N, N, N ', N'-tetramethyl-p-phenylenediamine 0.256 566 (4.11) 6.14 (4.13) 2. 2,5,10-tr imethyl-3-phenyl-5, 10-dihydrophenazine 0.260 494 (4.04) 614 (3.16) 666 (3.22) 730 (3.10) i
3. 5-ethyl-10-methyl-5,10-dihydrophenazine 0.264 450 (3.91) 606 (3.02) 660 (3.21) 726 (3.17) *. on
4. 5, 10-dimethyl-5, 10-dihydrobenzo (A) phenazine 0.264 532 (3.86) 670 (3.38) '
TABLE 8
E 1/2 Radical Cationic? max (log e) 1. 2,7-diphenoxy-5, 10-dimethyl-5, 10-dihydrophenazine 0.290 516 (4.11) 682 (3.40) 2. 2-phenoxy-5, 10-dimethyl-5, 10-dihydrophenazine 0.292 506 (3.99) 654 (3.32) 3. 2,7-bis (o-tolyl) -5,10-dimethyl-5,10-dihydrophenazine 0.292 512 (4.17) 680 (3.40) 744 (3.31) 4. 2,3-dimethyl-7-trifluoromethyl-5,10-diethyl-5,10-dihydrophenazine 0.292 482 (4.09) 652 (3.29) 716 (3.16) in 5. 5,10-dimethyl-5,10-dihydrophenazine 0.300 460 (3.97) 608 (3.11) 660 (3.27) 7.28 (3.21) 6. 2,3-diphenyl-5, 10-dimethyl-5, 10-dihydrophenazine 0.300 532 (4.04) 676 (3.30) 744 (3.10) 7. 2 , 7-diphenyl-5, 10-dimethyl-5, 10-dihydrophenazine 0.300 532 (4.13) 702 (3.52) 768 (3.50) 8. 2-vinyl-5,10-dimethyl-5,10-dihydrophenazine 0.300 484 (3.94) ) 670 (3.27) 734 (3.21) 9. 2-phenyl-5, 10-dimethyl-5, 10-dihydrophenazine 0.308 496 (4.00) 676 (3.31) 744 (3.23)
TABLE 9
E 1/2 Radical Cationic? max (log e)
1. 5,10-diisopropyl-5,10-dihydrofenazine 0.344 480 (3.94) 682 (3.23) 752 (3.19) 2. 5, 10-dimethyl-5, 10-dihydrodibenzo (A, C) phenazine 0.344 536 (4.02) 3. 1,5,10-trimethyl-2-phenyl-5,10-dihydrofenazine 0.348 496 (3.95) 714 (3.16) 772 (3.08) 4. 2,3,5,10-tetramethyl-7-trifluoromethyl-5, 10- dihydrofenazine 0.348 482 (4.04) 658 (3.08) 714 (3.05) 4 - 5. 2,3,5,10-tetramethyl-5, 10-dihydrobenzo (B) phenazine 0.352 436 (4.01) 534 (4.14)
In accordance with an important aspect of the present invention, Table 10 shows the results of combining various concentrations of many of the materials of Tables 1 to 9 in an electrochromic medium of an electrochromic device and the manner in which the concentrations of minus three electroactive materials are chosen to produce a device having a preselected perceived color. Because the anodic materials and the cathode materials themselves are chosen to have similar redox potentials, the electrochromic medium retains the predetermined perceived color in its electrochemically activated states during its normal range of voltages.
TABLE 10
in or
Al = 5,10-dimethyl-5,10-dihydrophenazine Cl = bis (tetrafluoroborate) of l, 1-bis (3-phenyl (n-propyl)) - 4,4'-dipyridyraz A2 = 2-phenyl , 5,10-dimethyl-5,10-dihydrophenazine C2 = 1, -dibenzyl-2,2 ', 6,6'-tetramethyl-4,4'-di? Iridinium bis (tetrafluoroborate) A3 = 2,3- diphenyl-5,10-dimethyl-5,10-dihydrophenazine C3 = bis (hexafluorophosphate) of l, -ethylene-4,4'-dimethyl-2,2'-dipyridinium A4 = 5-ethyl-10-methyl-5, 10-dihydrophenazine C4 = l, -dimethyl-4,4 '- (1, 3,5-triazine-2,4-diyl) dipyridinium A5 = 2,5,10-trimethyl-3-phenyl-5,10-diperchlorate -dihydrofenazine C5 = 1, -dimethyl-2- (3-phenyl (n-propyl)) - 4,4'-dipyridinium A6 = 2,7-diphenoxy-5,10-dimeti-5,10-bis (hexafluorophosphate) -dihydrophenazine
i Ul
The results of Table 10 are shown in terms of the color coordinates L * a * b * of the transmitted light when the electrochromic window devices are in their fully colored state. This is the state in which L * is a minimum, the chroma is at a maximum and a * and b * are in addition to a * = 0 and b * = 0 of origin (for the normal operation of the device). The electrochromic devices are manufactured using parallel, flat and separate sheets of glass coated on the surface facing each other with tin oxide doped with fluorine (coated glass TEC 15 available from Libbey-Owens-Ford of Toledo, Ohio). The separation between fluorine-doped tin oxide layers (cell separation is 137 microns.) At least one electrochromic window device is filled with a propylene carbonate solution containing each of the various millimolar concentrations (mM). ) and combinations of anodic material or materials and cathode material or materials for each row of table 10. The visible spectrum of the device in its transparent state without applied voltage is subtracted from the fully colored state, usually when 0.6 to 1.0 volts are applied. differences in the spectra are converted to color coordinates (Standard Illuminant A / 2 degrees) shown on the right side of the table by a standard method known in the art, and Y is also shown, the measure of brightness.
Referring specifically to row 7, an electrochromic medium comprising an anodic and a cathodic electrochromic material is shown whose relative concentration is found in commercially available electrochromic mirrors. In an electrochromic window with this electrochromic medium in a completely colored state, the color coordinates show a large negative value a * of the green appearance and a slightly smaller negative value b * or a certain blue appearance and the fully colored window appears colored green-blue-green. In addition to a particular note are the electrochromic window devices with the concentrations / combinations provided in rows 3 and 4 which have very low a * and b * absolute values and which appear almost perfectly gray, and the devices of the rows 12 and 14 which also show relatively small values for a * and b * and provide a gray appearance close to the neutral with various applied voltages and transmission levels that include the lowest transmission level or fully colored state. In Table 10, all of the anodic materials combined in a device have similar redox potentials to each other and all of the cathode materials combined in a device have similar redox potentials to each other. Therefore, the devices have the same color perceived through their coloration or darkening interval, it is
In other words, the devices lack color gradation both during coloring and in the clearance. It should be understood that with the data in Tables 1 to 10, not only the combinations of various anodic electrochromic and cathodic electrochromic materials can be chosen, but that various relative concentrations of each of the anodic materials and cathode materials can be chosen. The totality of such combinations of electrochromic materials thatWhen they are combined provide a gray device, it should be understood that they are within the scope of the present invention. Figure 2 illustrates a method by which a predetermined color can be chosen for an electrochromic medium. The absorption spectrum of visible light is determined for the colored state or, in this case, the cationic radical of each of the compounds included in the following for Figure 2. Each nominal spectrum is determined for the same path length and the concentration for the colored state of each material and scale as described below. As described above, in a stable electrochromic device, the amount of electrons added to the electrochromic medium is equal to the number of electrons removed during electrochemical activation and (as in the case for these materials included below for Figure 2), if the Electrochemical activation involves reduction of a
electron for each cationic compound and oxidation of one electron for each anodic compound, the total number or effective concentration of activated cathodic species will be equal to the total number or effective concentration of the activated anodic species. Therefore the percentages of the spectra for the cathodic species and the percentages of the spectra for the anodic species will each be added up to 100%. The Al curve shows 80% of the nominal spectrum of the cationic radical of 5,10-dimethyl-5,10-dihydrophenazine, curve A6 shows 20% of the nominal spectrum of the cationic radical of 2,7-diphenoxy-5,10-dimethyl- 5710-dihydrofenazine, curve C4 shows 50% of the nominal spectrum of the cationic radical of 1,1'-dimethyl-4,4 '- (1,3,5-triazine-2,4-diyl) dipyridinium diperchlorate and the curve C5 shows 50% of the nominal spectrum of the cationic radical of 1,1'-dimethyl-2- (3-phenyl (n-propyl)) -4,4'-dipyridinium bis (hexafluorophosphate). These scaled spectra are added together to provide the composite spectrum that would be essentially the same as that observed in an electrochemically activated electrochromic medium containing these relative concentrations of these electrochromic compounds. The absorbances in Figure 2 are shown on a relative scale as the absorbance of the electrochromic medium, once activated. They will have the same shape (or heights of relative peaks and peak positions) shown, but will
will increase in full as the voltage increases. As described above, the shape of the absorbance spectrum will remain the same across the normal voltage range of the electrochromic medium which is generally about 0.3 volts less than the difference in the redox potentials between the anodic materials and the cathode materials. approximately 0.2 to 0.4 volts more than the difference in these redox potentials. In this case, the normal operating voltage range across the medium for the materials in Figure 2 will be between about 0.35 volts to about 0.95 volts since the anodic materials have redox potentials of about +0.300 volts and the cathode materials have potentials redox of approximately -0.350 volts for a difference of 0.650 volts. Through this voltage range and the different levels of obscuration, an electrochromic window containing an electrochromic medium consisting of the electrochromic materials in FIG. 2 in the proportions of relative concentration given will maintain a constant appearance of blue-gray color. It can be said that the device maintains an almost constant tone as the magnitude of chroma increases. Figure 3 shows scaled spectra of: the cationic radical of 5,10-dimethyl-5,10-dihydrophenazine in curve A; the cationic radical of 2,3-diphenyl-5,10-dimethyl-5,10-
dihydrofenazine in curve B; A film of tungsten trioxide has been electrochemically reduced in the presence of lithium ion to form LixW03 in curve C. The sum or composite spectrum for the scaled spectra of these three electrochromic materials is shown in curve D. An electrochromic device containing this electrochromic medium has a W03 layer confined to the surface on an electrode (either the second or third surface) and a propylene carbonate solution containing the two anodic materials and a lithium salt (for example LiCl04 to provide ionic conductivity) and a lithium ion source), in contact with the other electrode and the W03 layer The spectra are scaled so that 60% of the anodic material will be electrochemically activated in 5, 10-dimethyl-5, 10-dihydrophenazine and 40% is 2, 3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine, and the thickness of the tungsten trioxide film is chosen to allow absorbance in its r state. educted to have a spectral contribution in relation to the anodic materials shown in figure 2. The electrochromic device is still self-eroding, similar to a device completely in solution phase, since oxidized anodic materials can diffuse into its trioxide film of reduced tungsten and spontaneously exchange electrons to oxidize the reduced film and reduce oxidized anodic materials. Therefore, the
Fully colored device will spontaneously return to its transparent condition even with an open circuit. The relative and total concentrations of these anodic materials which have similar redox potentials and the thicknesses of the tungsten trioxide layer can be chosen to provide a green-looking electrochromic device as illustrated by the spectrum in curve D. For this spectrum compound scaled to an L * value of 53.72, a moderate amount of coloration, the following color coordinates are obtained: a * = 2.18 and b * = -3.24 (for D65 / 2 degrees). This is a remarkable acquisition for devices based on tungsten trioxide which usually suffer from presenting a pure blue appearance to moderate coloration when the electrochromic medium includes tungsten trioxide as an electrochromic material. Similarly, the anodic material may be in the form of a surface confined layer, such as a metal oxide (including MxV205, NiOxHy / MxCe02, MxNb205, IrOx, together with Ce / Ti, Zr / Ce and mixed oxides of / Ce). An electrochromic device containing this electrochromic means has the layer confined to the surface on the second or third surface and a solution of two or more cathode materials, for example, viologens in a suitable solvent. The solution also contains a soluble ionic material (typically a lithium salt) in order to withstand the ionic conductivity
and to provide an ion source for intercalation of the confined layer on the surface. The relative and total concentrations of the cathode materials and the thickness of the anodic layer confined to the surface can be chosen to provide a preselected perceived color, including gray. For an electrochromic medium containing an electrochromic material of the electrodeposition type which is cathodic, two or more anodic materials can be combined in phase in solution of similar redox potential, in the medium in relative concentrations to produce a preselected perceived color appearance, including gray. The preselected relative concentrations of the anodic materials can be chosen on the basis of absorption spectra of the electrodeposited film, those of the anodic materials and the auto-deletion reaction rate. For an electrochromic material of the anodic electrodeposition type, two or more cathode materials with similar redox potentials can be combined in the electrochromic medium as described above to produce a preselected perceived color appearance, including gray. In general, the absorption spectra of the electrochemically activated states of electrochromic materials can be scaled and added in the manner discussed above to choose materials and relative concentrations that
provide an electrochromic medium with a particular perceived (and preselected) color through its normal operating voltage ranges. Although the invention has been illustrated using various types of electroactive and electrochromic materials, being able to preselect the perceived color is broad and applicable to electrochromic media consisting of organic, inorganic, organometallic and polymeric materials which can be electroactive and electrochromic materials in phase in solution, electrodeposition and confined on the surface, as well as combinations thereof. In certain applications such as architectural windows and mirrors in motor vehicles, the preselected color of the electrochromic medium may be different from that perceived as gray. In its broadest terms, a color that is perceived as gray is an achromatic color of luminance between black and white and, although achromatic, is defined as a perceived color that has zero saturation and therefore no hue, and must be constructed more broadly in the context of the present invention to mean a perceived color having little or moderate amount of chroma. Although the meaning of chroma will be understood by those familiar with the art, it may be useful to refer to the diagram L * a * b *. As stated in the above, in the diagram L * a * b * L * defines luminance, a * indicates the value
red / green and b * indicates the yellow / blue value. According to the present invention and as further described in the following paragraphs, a small or moderate amount of saturation is defined as a color of about (and including) a * = 0, and b * = 0, that is, that It perceives as gray when observed by human eyes under particular conditions. In its narrowest sense, the gray color can be defined by a circle around a * = 0 and b * = 0 that has a radius C * where C * = (a * 2 + b * 2) 12. Figure 4 shows the excursions in the color coordinate space a * b * (A / 2 degrees) for various electrochromic mirrors suitable for use as rear-view mirrors in motor vehicles. The excursions in the space of window color coordinates are generally very useful for choosing the electrochromic means for use in mirrors and vice versa, however, in contrast to the curves in figure 5 (discussed later) which are almost linear, the The curves of Figure 4 have a defined semi-elliptical shape. The reason for this is considered to be the following: the initial color coordinates for a mirror in its state of visual reflectance are determined primarily by the color imparted by the light by two passages through the substrate or glass substrates, the electrode or transparent electrodes and the non-activated electrochromic medium (each of which may have some light absorption of
light at some visible wavelengths) and a slight non-uniform reflectance (with respect to light of visible wavelengths), due to the transparent electrode or electrodes and to the reflecting layer or layers of the mirror. Therefore, electrochromic mirrors often appear slightly yellow or yellowish-green in their high-reflectance state and the color coordinates for all of the mirrors shown in Figure 4 are in the green-yellow quadrant (-a *, + b *) in a state of zero applied voltage of high reflectance. As the mirrors begin to darken when applying a voltage, and in this way decrease the transmission level of the electrochromic medium, the color coordinates of the reflected light are determined mainly by the color or the visible absorption spectra of the electrochromic medium. . This is shown in figure 4 by the excursion of the color coordinates in the green-blue quadrant (-a *, - b *) as the applied voltage increases. As the mirror continues to darken, the amount of light not absorbed by the two passages through the electrochromic device (which includes the electrochromic medium) begins to become comparable to the residual and secondary reflections due to the first surface of the front glass substrate, the interface between the front glass substrate
and the transparent electrode layer and the interface between the transparent electrode layer and the electrochromic medium. In general, these residual and secondary reflections are relatively colorless if the transparent electrode layer or layers are provided for color suppression of the transparent electrode structure (as is the case for the TEC15 glass available from TFO of Toledo, Ohio, or the neutral color coatings described in the co-filed and commonly assigned US patent application entitled "AN ELECTROCHROMIC MIRROR WITH TWO THIN GLASS ELEMENTS AND A GELLED ELECTROCHRO IC MEDIUM, the entirety of which description is hereby incorporated by reference. therefore, in this region of reflectance the color coordinates of the reflected light begin to be less dominated by the color or the visible light absorption spectra of the electrochromic medium and begin to be dominated by the relatively colorless residual and secondary reflections, and the curves in figure 4 begin to "turn over." As the reflectance continues decreasing, the color coordinates of the reflected light are dominated mainly by the color of the residual and secondary reflections and often point to relatively small absolute values of a * and b *. Therefore, at its highest applied voltage or lower reflectance levels, the color coordinates for the mirrors in Figure 4 (with the exception of
curve E) are still in the green-blue quadrant but are closer to a *, b * = 0, 0 compared to the intermediate reflectance levels. The desirability of an electrochromic mirror for use as a rear-view mirror of a motor vehicle, with respect to color, depends on the perceived color of the high-reflectance or transparent state; the perceived color of the lower reflectance state (at a frequency determined mainly by residual and secondary reflections); and the perceived color of the intermediate reflectance states. As stated in the foregoing, commercial electrochromic rearview mirrors typically have a slightly yellowish or yellowish-green tint in their high reflectance state with L * typically 90 ± 5, a * typically -4 ± 3 and b * typically 5 ± 3. Most desirable to many people would be an L * as high as possible and a * and b * as close as possible to zero. The current electrochromic mirrors which are used to obtain the color coordinate curves in FIG. 4 as a function of applied voltage are described below. The mirrors with color coordinates of curves A, B and D are constructed of two TEC 15 glass flat sheets, each 2.3 mm thick, joined together with an epoxy seal which provides a separation of 137 micrometers with oxide coatings. tin TEC 15 provided in the
surfaces 2 and 3. The mirrors have a fourth reflective surface consisting of a conventional silver overcoated copper reflector and paint layers applied to the rear surface of the TEC 15 glass sheet constituting the rear glass element. The mirror with the color coordinates of the F curve have a large exterior rear view mirror (approximately 12 centimeters high and 20 centimeters wide) which has front and rear glass elements that are 1.1 mm thick sheets of glass joined together by an epoxy seal which provides a separation of 180 micrometers between the surfaces 2 and 3. On the surface 2 is a color suppressed transparent electrode structure consisting of approximately 300A ITO, approximately 300A silicon dioxide, followed by approximately 1500A of ITO and the glass elements coated essentially colorless when observed both in transmission and in reflection. On the surface 3 there is a reflector electrode structure consisting of a first chromometal layer, an intermediate layer of metallic rhodium and an upper layer of silver-gold alloy which contains 85% silver and 15% gold, by weight. This reflector is essentially achromatic in appearance. In addition to the electrochromic materials described in the following, the electrochromic means of the mirror of the curve F also contains a polymeric matrix, which with the electrochromic solution,
forms a self-sustaining gel. The self-sustaining gel electrochromic medium is prepared in accordance with the teachings commonly assigned in co-pending US Patent Application Serial No. 08 / 616,967 entitled "IMPROVED ELECTHCHROMIC LAYER AND DEVICES COMPRISING SAME" for WL Tonar, et al. , whose full description of this patent application, including the references contained therein, are incorporated herein by reference. This mirror has a high end reflectance for the CIÉ curve of white light of 85%, a low end reflectance of 7% and an achromatic, "silver" or gray appearance with high, low and total intermediate reflectance levels. Curve A shows the color coordinates (A / 2 degrees) for various reflectance states of an electrochromic mirror having an electrochromic medium comprising: bis (tetrafluoroborate) of 1,1 '-bis (3-phenyl (n-propyl) )) -4, 4 '-dipyridinium 30 mM; 5, 10-dimethyl-5,10-dihydrofenazine 20 mM; and 2,4 mM 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine. Curve A has a maximum C * of 21.56 and a maximum of a * of -17.24. Curve B shows the color coordinates (A / 2 degrees) for various reflectance states of an electrochromic mirror having an electrochromic medium comprising: bis (tetrafluoroborate) of 1,1 '-bis (3-phenyl (n-propyl) )) -4,4 '- 30 mM bipyridinium, 5, 10-dimethyl-5,10-dihydrophenazine 18 mM and
7.2 mM 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine. Curve B has a maximum C * of 20.24 and a maximum of a * of -13.15. Curves C, E and D show color coordinates (A / 2 degrees) for the various reflectance states of commercially available electrochromic mirrors in Europe, the United States and around the world, respectively. Curve C has a maximum C * of 28.63 and a maximum of * -15.77, curve D has a maximum C * of 23.53 and a maximum of -20.48, and curve E has a maximum C * of 31.13 and a maximum to * of -16.84. The mirrors represented by curves A and B (2, 3-diphenyl-5, 10-dimethyl-5, 10-dihydrofenazine, 4 mM, and 7.2 mM, respectively), when observed at night in a colored vehicle, present a neutral gray appearance, while the devices shown in curves C and E have blue appearances, and the device shown in curve D has a green or green-blue appearance. This apparently is a small change in C * (the difference between 21.56 and 23.53 or 28.44) represents a significant change in the perceived color of the device. Curve F shows the color coordinates (A / 2 degrees) for the various reflectance states of an electrochromic mirror having an electrochromic medium comprising: 1, 1 '-dimethyl-2- (3-phenyl) bis (hexafluorophosphate) (n-propyl)) -4,4 '-dipyridinium 12 M; 1, 1 '-dimethyl-4,4' - (1,3,5-triazine-2,4-diyl) dipyridinium diperchloride 12 mM; 5, 10 -dimethyl-5, 10 -dihydrofenazine (DMP) 16 mM; and 2, 7-diphenoxy-5, 10-dimethyl-
, 10-dihydrofenazine 4 mM. Curve F has a maximum C * of 13.51 and a maximum a * of -7.48, and when observed at night in a motor vehicle provides a neutral gray appearance. Therefore, the difference in the perceived color of the mirrors that have a C * value of 21.56 and 23.53 (a change of 8%) is significant, while the difference in the perceived color of the mirrors that have a C * value of 13.51 and 21.56 (a change of 37%) both are perceived as gray. It seems clear that, in the narrowest sense, a color is perceived as gray for reflected front lamps when observed during the night activated in a motor vehicle when their color coordinates (A / 2 degrees) have a maximum value C * below of about 22, especially if the value a * is between -18 and zero. Although there is no certainty, it is generally considered that for the electrochromic rear-view mirrors for motor vehicles which darken at night, when the driver's eyes are at least partially adapted in the dark and mirrors which generally have their color perceived in the darkened state determined by the color of the light of the reflected front lamp, if there is a certain perceived color, the most preferred or acceptable color, whether for physiological or psychological reasons or not, are in the green-blue quadrant of space of color coordinates a *, b *. In fact, the acceptance of the mirror as relatively gray,
here the tolerance for excursions in -b * or the blue direction tends to be slightly greater than in the -a- or green direction, insofar as the value of C * is kept below a maximum value of approximately 22. This is extracted in figure 3 insofar as a mirror similar to that of curve D is perceived as slightly gray in the intermediate reflectance states (C * values close to maximum) during driving conditions at night with moderate dazzle. Mirrors which have color coordinate excursions during reflectance changes such as curves A and B are perceived much closer to gray, even at intermediate reflectance levels, while mirrors with curves C and E are perceived in a definite manner as blue in their intermediate reflectance states. It has been determined that, for drivers of motor vehicles at night, the perception will be that the mirror essentially gray through its reflectance range if it has a maximum value C * of less than about 22, especially if the value a * is between -18 and zero. It has also been determined that curve a is considered the limit of acceptability for a mirror perceived as green in its states of intermediate reflectance and the mirrors of curves B and F are considered essentially neutral or gray across its entire range of reflectance
Almost all electrochromic mirrors have most of their excursion of color coordinates in the green-blue quadrant. This may not be a total match since mirrors that have color coordinate excursions in the a-squares (red) and -b * (blue) during their reflectance changes may appear purple, which provides a frightening sensation to the drivers using these mirrors during dazzling conditions at night. The mirrors that have the color coordinate excursions in the quadrant -a * (green) and + b * (yellow) are considered undesirable by drivers and have difficulty in being sufficient in reflectance to alleviate a strong flash. This is the same reason why a dark yellow window still has a significant light transmission. There is a certain way of thinking that mirrors with an excursion of color coordinates in the quadrant + a * (red and + b * (yellow) (especially with values + a * greater than the values + b *) might be desirable for some drivers who like the red or orange-like display lighting in a motor vehicle but in general the mirrors with this type of color coordinate excursion are controversial, therefore the a-quadrant is preferred (green) and -b * (blue) for the color coordinates of the rear-view mirrors in their reflectance states
intermediate, specifically if C * and a * are limited as described in the above. Figure 5 shows color coordinate excursions (D65 / 2 degrees) for four electrochromic windows in curves A to D (each made with TEC-15 glass with a cell separation of 137 micrometers) and curve E shows the excursions of color coordinates (D65 / 2 degrees) for the composite spectrum of Figure 2 multiplied by several factors to simulate various L * values or transmission levels. Each of the experimental electrochromic windows, the spectrum of the window at 0.0 volts is subtracted from the spectrum at each applied voltage so that the color coordinates are calculated essentially for the electrochromic medium alone. Curve A is for an electrochromic window containing a propylene carbonate solution of 28 mM 5,10-dimethyl-5,10-dihydrophenazine and 1, 1'-bis (3-phenyl) (n-propyl) bis (tetrafluoroborate). )) -dipyridinium 34 mM. As the voltage applied to the window increases from 0.0 volts to 1.0 volts, the color coordinates for the light transmitted by the medium change from L *, to *, b * of 100, 0, 0 to a slightly gray appearance and slightly blue with an L *, a *, b * of 40.14, -36.47, -5.87. Simply using straight lines to connect the data points to the various voltages results in a relatively straight general line, and
for this electrochromic medium containing only two materials the color or dye remains consistent throughout the normal voltage and transmission range of the device. Curve B shows the color coordinate data for an electrochromic medium for which it is desired to produce a window with a bright green appearance. The window was filled with a propylene carbonate solution of 25 mM 5,10-dimethyl-5,10-dihydrophenazine, 1, 1'-dibenzyl-2, 2 ', 6,6'-tetramethyl bis (tetrafluoroborate). -4,4 '- 10 mM dipyridinium and bis (hexafluorophosphate) of 1, 1' -ethylene-4,4 '-dimethyl-2,2' -dipyridinium 20 mM. As can be seen from curve B, this electrochromic medium changes from L *, to *, b * equal to 100, 0, 0 or colorless to 0.0 volts, up to L *, a *, b * equal to 64.12 , -40.58, 35.17 to 1.0 volts. Because the two cathode materials have a similar redox potential, although they have significantly different absorption spectra, the medium has the same apparent bright green color or consistent tone through its normal voltage and transmission range. Curve C is for an electrochromic window filled with a propylene carbonate solution of 5, 10-dimethyl-5, 10-dihydrofenazine 20 mM, 2,3-diphenyl-5, 10-dimethyl-5, 10-dihydrophenazine 4 mM and bis (tetrafluoroate) of 30 mM 1,1 '-dimethyl-4,4' - (1, 3, 5-triazin-2,4-diyl) -dipyridinium. This electrochromic medium has a consistent tone with a perceived color
red / brown through its normal voltage and transmission interval which touches the color coordinates for the medium from L *, a *, b * equal to 100, 0, 0 to 0.0 volts, up to L *, a *, b * equal to 53.70, 9.44, 9.70 to 1.0 volts. Curve D shows what happens if the relative concentration of anodic materials in curve C is reversed. The window for curve D is filled with a propylene carbonate solution of 5, 10-dimethyl-5, 10-dihydrofenazine 4 mM, 2,3-diphenyl-5, 10-dimethyl-5, 10-dihydrofenazine 20 mM and 1, 1 '-dimethyl-4,4' - (1,3,5-triazin-2,4-diyl) -dipyridinium bis (tetrafluoroborate) 30 mM. This medium, with its relative concentrations inverted compared to the window of the curve C; presents a consistent tone with a red / magenta color perceived through its normal voltage and transmission intervals which touch the color coordinates from L *, a *, b * equal to 100, 0, 0 to 0.0 volts, to a L *, a *, b * equal to 43.70, 45.23, -27.19 to 1.0 volts. Curve E shows color coordinates for the composite spectra of Figure 2 multiplied by various factors constituting the L * value calculated for the various spectral changes scaled through a range of L * values similar to that of the experimental devices of the curves A to D. At the highest absorbance, the color coordinates L *, a *, b * are equal to 26.91, -3.62 and -16.2. This medium has relatively small absolute values of a * and
b * although the value of L * is very low. This small excursion in a *, b * for a large change in L * is indicative of a relatively gray medium. An experimental window with an electrochromic medium containing the electrochromic materials in the same relative concentrations shows an excursion of color coordinates that is in excellent agreement with the excursion of the theoretical or calculated medium of Figure 2 and the experimental device, as expected from the teachings of this invention, it has a gray appearance with a slight blue-gray tint. For color coordinate curves like those in Figure 5, it is interesting to note that a window containing the same electrochromic medium as a mirror will typically have a larger color coordinate excursion since the residual reflections that come into play in the Mirrors are not a significant factor in the apparent color of transmitted light for windows in their activated states. However, the excursion of color coordinates for the windows is certainly valuable for designing electrochromic means for mirrors and vice versa. A general observation is that the more gray a window appears when it is colored, the smaller its color coordinate excursion from a *, b * equal to 0, 0 for coloration to a given L * value. The curves in Figure 5 are almost straight lines but show some curvature. This is not unexpected because the places
Constant-tone Munsell as a function of increasing chroma show some curvature, see, for example, the figure on page 63 and the associated discussion in Billmeyer and Saltzman ibid. Although some of the combinations of electrochromic materials maintain a very consistent color or perceived tone even when the redox potentials are not similar, many do not. Figure 6 shows the color coordinate curves (D65 / 2 degrees) for three windows showing varying amounts of graduation. Curve A of FIG. 6 is for an electrochromic medium in an electrochromic window filled with a propylene carbonate solution of 30 mM 5,10-dimethyl-5,10-dihydrophenazine, 1,1'-bis (tetraf luoroborate) bis (3-phenyl (n-propyl)) dipyridinium 15 mM and bis (hexafluorophosphate) of 1,1'-ethylene-2,2'-dipyridinium 15 mM. This last compound has a redox potential of -0.252 on the redox potential scale of the compounds of Tables 1 to 9. The curve A starts with a *, b * equal to 0.0 to 0.0 volts and higher voltages show more curvature compared to the curves in Figure 5. For the window of curve A, there is very little perceived change in color tone or appearance as a function of voltage. This is because the difference in the redox potential between the two cathode materials is 44 millivots so that they are still similar within the definition of this invention.
The electrochromic medium for which curve B data was measured is contained in an electrochromic window filled with a propylene carbonate solution of 8 mM, 5,10-dimethyl 5-ethyl-10-methyl-5,10-dihydrophenazine solution. -5, 10-dihydrodibenzo (A, C) phenazine 20 mM and bis (hexafluorophosphate) of 1, 1 '-ethylene-4,4' -dimethyl-2, 2'-dipyridinium 34 mM. The curve of color coordinates shows a significant curvature and the device shows easily differentiable perceived colors ranging from grayish / yellow to low voltage, reddish / brown at high voltages. The difference in the redox potential between the two anodic materials is 80 millivots and the graduation is easily evident. Curve C shows data for an electrochromic medium in an electrochromic window filled with N, N, N ', N'-tetramethyl-p-phenylenediamine 8 mM, 5, 10-diisopropyl-5, 10-dihydrofenazine 20 mM and bis (tetrafluoroborate ) of 34 mM 1,1 '-bis (3-phenyl (n-propyl)) -dipyridinium. The redox potentials of anodic materials differ by 88 millivolts and the color coordinate curve shows a significant curvature. The perceived color of the device changes only slightly from blue to blue-purple through the applied voltage range. The slight variation perceived in the color or variation of dye may be due to the fact that, at the voltages where the absorption spectra change shape, the magnitude of the
chroma is already very high and L * is very small, so the change in tone is obscured. The electrochromic medium comprises electrochromic materials, and other materials such as solvents, light absorbing substances, light stabilizers, thermal stabilizers, antioxidants and self-sustaining gel (which includes a polymeric matrix). The polymeric matrix that can be optionally used in the present invention is a part of the self-sustaining gene which is described in commonly assigned co-pending US patent application serial number 08 / 616,967, entitled "IMPROVED ELECTROCHROMIC LAYER AND DEVICES COMPRISING SAME "for WL Tonar et al. For electrochromic mirrors, the self-sustaining gel interacts cooperatively with the glass elements 112 and 114 to produce a mirror that acts as a thick unitary member instead of two glass elements held together only by a seal member. This allows one to build a rear view mirror with a thinner glass in order to decrease the overall weight of the mirror and at the same time maintain sufficient structural integrity so that the mirror will survive the extreme environment common in the automotive environment. For electrochromic windows (especially larger windows), the polymeric matrix interacts interactively with the glass elements 112 and 114 so that the hydrostatic pressure that typically occurs
by gravity acting on the electrochromic medium (when the electrochromic medium includes a solution) it is reduced or eliminated. During the operation of an electrochromic mirror in the transparent state and having a third surface reflector, the light rays entering through the front glass 112 and passing through the transparent conductive layer 116, the electrochromic medium in the chamber 122 before being reflected by the reflector / electrode placed on the third surface 114a (unless the mirror has a fourth reflecting surface) of the mirror 110. The light in the reflected rays comes out by the same general path traversed in the reverse direction. When a sufficiently high voltage is applied (in some cases of the appropriate polarity) to an electrochromic device, an electrochromic reduction takes place by transfer of electrons to the electrochromic medium from one of the electrodes (called the cathode) and electrochemical oxidation takes place. by electron transfer from the electrochromic medium to the other electrode (referred to as the anode). The electrochemical reduction and / or the electrochemical oxidation give rise to a change in the absorption properties of the light of the reduced and / or oxidized material or materials. The operation, or activation of the device generally results in an increase in the absorption of light at the wavelengths of interest (although
it is possible for operation of an already colored device that results in a decrease in the absorption of light at the wavelengths of interest). When the device is in its dark state or in some state between its dark and transparent state, both the incoming rays and the reflected rays are attenuated in proportion to the degree to which the light is absorbed by the electrochromic means 124. Those familiar with the art will understand that the main difference between an electrochromic motor vehicle mirror and an electrochromic window or some other electrochromic device is the intrusion of a reflector by mirrors. By following the teachings established within the specification, an electrochromic device can be manufactured that has several preselected perceived colors, including gray, when that device is a mirror, window, screen, etc. With respect to motor vehicle mirrors, FIG. 7 shows a front elevational view schematically illustrating a mirror assembly 110 and two mirror assemblies Illa and llb and rearview mirror lllb for the driver's side and the driver's side. passenger, respectively, all of which are adapted to be installed in a motor vehicle in a conventional manner and where the mirrors are oriented towards the rear of the vehicle and can be seen by the driver of the vehicle to provide a
back view. Within the mirror assembly 110, and outside of the Illa and IIIb assemblies of the rear view mirror, light-sensing electronic circuits of the type illustrated and described in the aforementioned Canadian Patent No. 1,300,945 may be incorporated; U.S. Patent No. 5,204,778, or U.S. Patent No. 5,451,822, and other circuits capable of detecting flashes and ambient light, and of supplying an activation voltage to the electrochromic element. Mirror mounts 110, Illa and IIIb are essentially identical and like numbers identify components in the interior and exterior mirrors. These components may be slightly different in configuration but work substantially in the same way and generate substantially the same results as the components with similar number. For example, the shape of the front glass element of the interior mirror 110 is generally larger and narrower than the exterior mirrors Illa and IIIb. There are also certain different operating standards established on the interior mirror 110 as compared to the exterior mirrors Illa and IIIb. For example, the interior mirror 110 generally, when completely clean, should have a reflectance value of about 70 percent to about 80 percent or greater, while the outside mirrors often have a reflectance of about 50 percent to about 65 percent.
In addition, in the United States (as provided by the automobile manufacturers, passenger-side mirror IIIb typically has a spherical curvature, or convex shape, while the driver's side mirror Illa, and interior mirror 110 must currently be In Europe, the Illa mirror on the driver's side is commonly flat or spherical, while the mirror lllb on the passenger side has a convex shape.In Japan, both mirrors have a convex shape.The following description is generally applicable to all The mirror assemblies of the present invention The electrical circuit preferably incorporates an ambient light sensor (not shown) and a glare light sensor 160, the glare sensor is positioned either behind the mirror glass and directed to Through a section of the mirror with the reflective material completely or partially removed, or the glare sensor can be placed outside of the reflective surfaces, for example, in the visor 144. Additionally, an area or areas of the electrode and the reflector, such as number 146 or the area aligned with the sensor 160 can be completely removed, or partially removed, by example, in a dot pattern or lines, to allow a fluorescent vacuum display, such as a compass, watch or other signs to show the vehicle driver. The patent application
of the United States copendiente referred to above entitled "AN INFORMATION DISPLAY AREA ON ELECTROCHROMIC MIRRORS HAVING A THIRD SURFACE REFLECTOR" shows a currently preferred pattern of lines. The present invention is also applicable to a mirror which uses only a video chip light sensor to measure both glare and ambient light and which is also capable of determining the direction of glare. An automatic mirror inside a vehicle, constructed in accordance with this invention can also control one or both exterior mirrors as slaves in an automatic mirror system. The rear view mirrors including the present invention preferably include a visor 144 which extends around the entire periphery of each individual assembly 110, illa and / or lllb. The visor 144 matches and protects the spring clips (not shown) and the peripheral edge portions of the sealing member and the front and rear glass elements (described below). A wide variety of visor designs are known in the art, such as, for example, the visor described and claimed in the aforementioned U.S. Patent No. 5,448,397. There is also a wide variety of housings well known in the art for attaching the mirror assembly 110 to the interior front windshield of an automobile, or for attaching the mirror assemblies Illa and III to the exterior of an automobile.
A preferred housing for attaching an interior assembly is described in the aforementioned U.S. Patent No. 5,337,948. The materials described in Examples 1 to 29 are considered to be novel chemicals except for the chemical substance of Examples 10 and 25. Certain properties of some of these materials are shown in Tables 1 to 9. These materials can be used as redox materials in applications such as redox batteries, redox indicators and mediated electron transfer, in electro-organic synthesis. Because they significantly change their absorption spectra by visible light in the face of electrochemical reduction or electrochemical oxidation, they are also useful in electrochromic media for use in electrochromic windows, screens, mirrors, etc. In particular, these materials have absorption spectra of colored state and redox potentials so that they can be placed in groups of materials with similar redox potentials. By selecting two or more materials with absorption spectra of different colored states from a group with similar redox potentials, and by choosing the relative concentrations of two or more materials, an electrochromic medium having a preselected perceived color can be designed when incorporates into an electrochromic device and is operated through a range of
normal voltage or device transmission interval. These materials are also particularly useful in the design of electrochromic media that result in electrochromic devices that have a perceived color of gray through their normal ranges of operation. Many of the phenazine compounds included in Tables 7 to 9 present the following general structure:
[XX]
and present advantageous characteristics in comparison with phenazines previously studied for inclusion in electronic media. Most of the phenazines studied previously have their main visible light absorption peak with their wavelength for maximum absorbance approximately 460 nanometers for the electrochemically activated state. The combination of a phenazine compound as the anodic material with a typical salt of 1, 1 '-substituted, 4, 4' -dipyridinium as the cathode material (with a length
of wave for a maximum absorbance of visible light of approximately 600 nanometers for the electrochemically activated state), produces an electrochromic medium which is poorly absorbed in the wavelength range from about 470 to about 540 nanometers. These media and devices typically contain a green-blue-green appearance in daylight and a somewhat grayish-blue appearance when used in a rear-view mirror to relieve glare during nighttime driving. Phenazine compounds having a substantial visible light absorbance in the range of 470 to 540 nanometers have been discovered and, in fact, have a maximum visible absorbance peak in this range. Of particular interest are phenazine compounds with phenyl, phenoxy, vinyl or substituted phenyl eg tolyl, in one or more of positions 2, 3, 7 and 8. Notably, the normally-used aryl groups included above have little or no no effect on the redox potential of the first oxidation of an electron of these compounds when they are substituted in these positions, and even these groups present a redshift of the absorption spectra of the oxidized or electrochemically activated state. Combining these novel phenazines at various relative concentrations with phenazines that absorb approximately 470 nanometers or less results in an electrochromic medium having a desirable color appearance,
including gray, when activated. In addition, phenazine compounds with a substitution of aryl group, for example phenyl, vinyl, tolyl, etc., in one or more of positions 2, 3, 7 and 8 can be combined in electrochromic media without having an impact on photochemical stability or thermal media. The only potential drawback is that the neutral non-activated state of these compounds may be slightly yellow due to the persistence of UV absorbance of the non-activated state. This concern is largely solved by placing a methyl or alkyl group or groups adjacent to or on the aryl substituent, or on the aryl group at a position adjacent to the linkage between the phenazine and the aryl group. For example, 2, 5, l? -trimethyl-3-phenyl-5,10-dihydrophenazine; 1,5,10-trimethyl-2-phenyl-5,10-dihydrophenazine; 2, 7-di (s-tolyl) -5, 10-dimethyl-5, 10-dihydrophenazine and even 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine (two adjacent aryl groups) are colorless or less yellow than 2-phenyl-5,10-dimethyl-5,10-dihydrophenazine, 2,7-diphenyl-5,10-dimethyl-5,10-dihydrofenazine and 2-vinyl-5,10-dimethyl-5 , 10-dihydrofenazine. Other phenazines with maximum absorption wavelengths in the range of 470 to 540 nanometers for their electrochemically activated state, without being substantially yellow in their non-activated state, are very useful as well as for combinations that obtain a preselected color, especially gray ( by
Example 2, 7-diphenoxy-5,10-dimethyl-5,10-dihydrophenazine; 2-phenoxy-5, 10-dimethyl-5,10-dihydrophenazine; and 5, 10-diisopropyl-5,10-dihydrophenazine). In Example 17, 5, 10-dimethyl-5, 10-dihydrofenazine is made from phenazine in a novel synthesis in a container. The same strategy can be applied to the alkylation of phenazines, triphenodithiazines, triphenoxazines, quinoxalinophenazines, phenazine-based dyes, phenoxazine-based dyes, phenothiazine-based dyes and similar phenazine compounds. In the general procedure, the general material azine is reduced and alkylated in the same reaction mixture. This method is novel because it describes how to carry out the alkylation reduction of the azine compound in a safe, fast and cost-effective manner, in a reaction in a vessel. In the previous literature there are references to reduce and rent phenazines in separate stages and usually one of the stages is dangerous and expensive. In the reference, "The Direct Preparation of Some Dihydro and Other Phenazine Derivatives," JACS (1975) p. 6178-6179, phenazine is reduced with sodium or potassium metal and then alkylated with methyl iodide. This method is dangerous, tedious and expensive. In another reference, "Preparation and Properties of Electron Donor Acceptor Complexes of the Compounds Having Capto-dative
Substituents, "J- Heterocvclic Chemistry (1989), Vol. 26, pp. 433-438, phenazine is reduced with sodium hydrosulfite The resulting dihydrophenazine is then alkylated by using butyllithium for a lithium-potron exchange, and the adduct and lithium is alkylated with addition of methyl iodide This process is a synthesis of two vessels involving a dangerous alkylation step In accordance with one embodiment of the present invention, the azine compound, the reducing reagent, the base, the alkylating reagent and phase transfer catalyst are added together in a polar aprotic solvent with a small amount of water present.When heating occurs, azine is reduced and alkylated.We have applied our process to manufacture many alkylated phenazines, by Example 2, 7-diphenyl-5,10-dimethyl-5,10-dihydrophenazine, nitrogen heterocycles, for example, N, N ', N ", N" -tetrabutylquinoxalinophenazine; r example 3, 7-dibutoxy-10-butylphenoxazine from 7-hydroxy-3H-phenoxazin-3-one. Typically we have used sodium hydrosulfite as the reducing reagent, however, other reducing reagents can also work well, for example hypophosphorous acid. Our base is usually potassium carbonate or sodium carbonate powder. Alkylating reagents can be iodides, bromides, chlorides, triflates,
alkyl mesylates or tosylates. The phase transfer catalyst is essential and we have had good success with quaternary ammonium halides or hydrogen sulphates. Corona ethers and quaternary phosphonium catalysts also work well. The best catalysts that have proven to be "accessible" are quaternary ammonium salts which are a familiar term for those familiar with the technique of phase transfer reactions. The best solvent is acetonitrile, but other polar aprotic solvents can work. It is also useful to decrease the reaction times by adding a small amount of water. The procedure is as follows: For one mole of azine compound having two azine nitrogens, the amounts of the other reagents used are: 1.15 moles of sodium hydrosulfite (85%), 2.0 moles of sodium carbonate, 4.0 moles of halide alkyl, 0.115 moles of phase transfer catalyst, 10 liters of acetonitrile and 200 milliliters of water. All reagents are combined in a vessel and heated to reflux under an inert atmosphere for a minimum of 5 hours. 10 liters of water are added and the alkylated product is filtered off. These are currently the preferred quantities of these reagents, however, our intention is to show that, because the reaction is robust, these reagents will work to produce
the alkylated product, even when the amounts of reagents are not present in the preferred amounts. An alteration of these conditions is necessary when alkylamino substituents are present. In this case, a two-phase reaction consisting of a non-polar organic solvent and an aqueous hydroxide layer is replaced by the acetonitrile / water / carbonate combination in the aforementioned process. This prevents the quaternary formation or quaternization of the dialkylamino groups. It is also important to note that alkyl iodides are more reactive than alkyl bromides and alkyl bromides are more reactive than alkyl chlorides. Sodium iodide can be added as a cocatalyst when alkyl bromides or alkyl chlorides are used. In conclusion, this process of reduction / alkylation in a container is widely applicable for the rental of phenazines and related azine compounds, as shown in examples 1, 3, 4, 12, 13, 14 and 16. The dipyridinium compounds included in the Tables 1 to 6 are commonly referred to as viologens. In order to revert to the most difficult to reduce electrochemically viologens, it is known to replace the dipyridinium salts with alkyl groups in one or more of the 2, 2 ', 6 and 6' positions shown in the following general structure .
x
[XXX]
However, substitution with methyl groups in one or more of the 2, 2 ', 6 and 6' positions leads to compounds with relatively acidic protons due to the strong electroattracting power of the quaternized nitrogen near the methyl group. In addition, the 1, 1 ', 2, 2', 6,6 '-hexamethyl-4,4'-dipyridinium salts are only slightly soluble in polar organic solvents such as cyclic esters and nitriles when the salt contains anions such as tetrafluoroborate, hexafluorophosphate , perchlorate or halides. Example 29 describes the synthesis of viologens that overcome these difficulties and provide compounds that have diffusion characteristics that are desirable. The compounds of structure XXX with one or more of the 2, 2 ', 6 and 6' positions substituted with aralkyl group or groups, for example 2-phenylethyl and 3-phenyl (n-propyl), or an alkyl group or groups of long chain, for example hexyl, which have the other positions 2, 2 ', 6 and 6' substituted
with methyl group or groups have increased solubility in polar organic solvents in comparison with compounds of structure XXX which have methyl groups in each of the 2 positions, 2, 6 and 6 '. In general, the substitution of one or more of positions 2, 2 ', 6 and 6' with 2-phenylethyl or 3-phenylpropyl results in a viologen which is more difficult to reduce electrochemically, does not have a proton or protons so acidic compared to whether the substitution was a methyl group and because phenyl groups are considered to be well solvated by solvents such as propylene carbonate, these compounds are considered to have lower diffusion coefficients compared to similar viologens without these substitutions. Certain aspects of the present invention are illustrated in greater detail in the following examples. Unless otherwise specified, all concentrations mentioned in the examples are at room temperature (20-27 degrees Celsius) and all temperatures are in degrees Celsius.
Use 1
Synthesis of 5-ethyl-10-methyl-5, 10-dihydrophenazine
It is prepared as follows 5-ethyl-10-methyl-5,10-dihydrophenazine: The 5-methylphenazinium methosulfate salt is reduced and alkylated to 5-ethyl-10-methyl-5,10-dihydrophenazine in a transfer reaction phase of a container. 1.0 grams of 5-methylphenazinium methosulfate are refluxed in a 2-phase suspension containing 50 milliliters of toluene, 10 milliliters of 4M aqueous NaOH, 10 grams of sodium hydrosulfite, 10 milliliters of iodoethane, 0.1 grams of sodium sulfate, tetrabutylammonium and 50 milliliters of water. This mixture is refluxed for 4 days after which the reaction is cooled and the lower aqueous layer is separated and discarded. After two additional washings with water, the toluene is removed and the untreated product is redissolved in 50 milliliters of hot ethanol. The cooled solution produces 0.35 grams of 5-methyl-10-ethyl-5,10-dihydrofenazine for a yield of 48%.
? 2
Synthesis of 2-vinyl-5, 10-dimethyl-5, 10-dihydrophenazine
A sample of 2-formyl-5,10-dimethyl-5,10-dihydrofenazine is prepared according to the procedure of Pokhodenko et. al., J. Chem. Soc. Chem. Commun, 1985, 72. The formyl group is converted to the vinyl group by the procedure of Ghosh and Spiro J. Electrochem. Soc, 128, 1281 (1981) to make 4-vinyl-1, 10-phenanthroline. Recrystallization from acetone / water gives a yellow solid with a mass 236 and an electrochemistry consistent with a N, N'-dialkylated phenazine.
Example 3
Synthesis of 2,7-bis (o-tolyl) -5,10-dimethyl-5,10-dihydrophenazine
2,7-bis (o-tolyl) -5,10-dimethyl-5,10-dihydrophenazine is prepared from 2,7-dichlorophenazine. The 2,7-dichlorophenazine is prepared from 2-iodo-5-chloronitrobenzene and 2-nitro-5-chloroaniline using an Ullmann type aryl amination followed by reduction of the nitro groups and oxidation with ferric chloride.
The o-tolyl groups are substituted by the chloro group in 2,7-dichlorophenazine with a "Suzuki coupling" using o-tolylboronic acid. "Palladium Catalyzed Cross-Coupling Reactions of Organoboron Compounds", N. Miyawra and A. Suzuki, Chem. Rev. 95, p. 2457-2483 (1995). This cross-coupling reaction requires approximately 3 weeks for it to be carried out. The 2,7-bis (o-tolyl) phenazine (2.2 grams) is refluxed in acetonitrile containing 2% by volume of water, 0.6 grams of methyltributylammonium chloride, 8.7 grams of sodium hydrosulfite, 1.6 grams of sodium carbonate. sodium and 3.1 milliliters of iodomethane. After 40 hours, water is dripped into the reaction solution at reflux and the product is separated by precipitation. After cooling, the product is filtered off and recrystallized from acetonitrile. 2.07 grams of product are isolated for an 87% yield for alkylation.
Example 4 Synthesis of 2,3-dimethyl-7-trifluoromethyl-5,10-diethyl-5,10-dihydrophenazine
2, 3-dimethyl-7-trifluoromethyl-5, 10-d i e t i 1 f e n a z a n a a p a r t i r of 2, 3-d i me t i 1 - 7 -trif luoromethyl f enazine is prepared.
2,3-Dimethyl-7-trifluoromethylphenazine is prepared in a 3-step process, starting with 4,5-dimethyl-1,2-phenylenediamine and 3-nitro-4-bromobenzotrifluoride. The nucleophilic substitution product is diarylamine which is then reduced with stannous chloride in concentrated HCl to diaminodiphenylamine. This compound is oxidized to phenazine with ferric chloride, and a dilute aqueous solution of HCl. Tomlinson: "The Preparation of 2: 2 '-diaminofiphenyl Amines", J. Chem. Soc. , pp. 158-163 (1939). 24.0 grams of this phenazine are added to 500 milliliters of acetonitrile, 21.2 grams of sodium carbonate, 69.6 grams of sodium hydrosulfite, 3.4 grams of tetrabutylammonium acid sulfate and 78.0 grams of iodoethane. This mixture is refluxed for 4 days before it is complete. 400 milliliters of water are slowly added to the reaction suspension at reflux. The desired product is separated by precipitation and, after cooling, it is filtered off. The product is recrystallized from hot ethanol which provides 17.7 grams of 2,3-dimethyl-7-trifluoromethyl-5,10-diethyl-5,10-dihydrophenazine. This provides a general yield of 30.1% from 4,5-dimethyl-1,2-phenylenediamine.
Example 5 Synthesis of 2, 3, 5, 10-tetramethyl-7-trifluoromethyl-5, 10-dihydrophenazine
This material is prepared by the synthesis procedure of Example 4 with the exception that the iodomethane is replaced with iodoethane in the alkylation step.
Example 6 Synthesis of 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine
2,3-diphenylphenazine is prepared according to the method of C. H. Issidorides, et. al., Tetrahedron 34, 217 (1978). The phenazine nitrogens are then methylated by the procedure of Synthesis Example 3.
Example 7 Synthesis of 2, 5, 10-trimethyl-3-phenyl-5,10-dihydrophenazine
2-Methyl-3-phenylphenazine is prepared by the method of C.H. Issidorides, et al., Tetrahedron 34, 217 (1978), except that 1-phenyl-1,2-propanedione is replaced by benzyl. The phenazine nitrogens are then methylated by the procedure of Synthesis Example 3.
Example 8 Synthesis of 5,10-diisopropyl-5,10-dihydrophenazine
Shake 9.0 grams of phenazine with 6.5 grams of a finely divided metal alloy of 10: 1 potassium and sodium in 150 milliliters of 1,2-dimethoxyethane at 40 ° C until a brick-red suspension forms: approximately 24 hours . 14.1 milliliters of 2-bromopropane are added and the reaction is allowed to stir for 2 hours at which time the reaction mixture is filtered, the filtrate is rotoevaporated to dryness and the product is loaded as a solid onto a column of Silica gel. The column is prepared with, and eluted with 8: 2 hexane / ethyl acetate. Removal of the solvent from the target compound fractions provides a white solid which recrystallizes from methanol to provide 2.1 grams of white needles, m.p. 80-81 ° C. A mass of 306 is confirmed by mass spectrometry.
Example 9 Synthesis of 2, 3, 5, 10-tetramethyl-5, 10-dihydrobenzo (B) phenazine
2,3-dimethylbenzo (B) phenazine is prepared by the condensation of 2,3-diaminonaphthalene with 4,5-dimethyl-1,2-benzoquinone in 4: 1 ethanol and acetic acid at reflux
for 2 hours. Phenazine is alkylated by the procedure of Synthesis Example 8, using iodomethane. The electrochemical analysis is consistent with a N, N'-dialkylated phenazine.
Example 10 Synthesis of 5, 10-dimethyl-5, 10-dihydrodibenzo (A, C) phenazine
Dibenzo (A, C) phenazine is prepared with 1,2-phenylenediamine and phenanthrenequinone, using standard condensation conditions. Dibenzo (A, C) phenazine, 4.2 grams, is alkylated by the procedure of synthesis example 8 using methyl iodide to provide 2.1 grams of yellow crystals. In electrochemical analysis it is consistent with a N, N'-dialkylated phenazine.
Example 11 Synthesis of 5, 10-dimethyl-5, 10-dihydrobenzo (A) phenazine
Benzo (A) phenazine is prepared with 1,2-phenylenediamine and 1,2-naphthoquinone, using standard condensation conditions. This phenazine is reduced with a 3: 1 potassium / sodium metal alloy in dimethoxyethane to a brick-red alkali metal adduct. Alkylation occurs
for 1 hour with the addition of iodomethane. The residual KI / Na alloy is suspended with the addition of ethanol. The product is isolated by column chromatography and recrystallized from ethyl acetate / hexane. 2.0 grams of the product are isolated for a total yield of 38%.
Example 12 Synthesis of 2-phenoxy-5,10-dimethyl-5,10-dihydrophenazine
2-Phenoxy-5,10-dimethyl-5,10-dihydrofenazine is prepared from 2-chlorophenazine. 2-Chlorophenazine is prepared using 4-chloro-l, 2-phenylenediamine and l-iodo-2-nitrobenzene. This diphenylamine is reduced with stannous chloride to chloro-2,2'-diaminodiphenylamine and oxidized to 2-chlorophenazine with ferric chloride in dilute aqueous HCl. "Tomlison: The Preparation of 2, 2 '-Diaminodiphenylamines," J. Chem. Soc., 158-163 (1939). 2-chlorophenazine is reacted with potassium phenolate in tetraglime to reach 2-phenoxyphenazine. 150 milligrams of 2-phenoxyphenazine in 50 milliliters of acetonitrile, 3 milliliters of iodomethane, 1.7 grams of sodium hydrosulfite, 0.21 grams of sodium carbonate and 0.1 grams of tetrabutylammonium acid sulfate are refluxed. After 24 hours, the reaction ends. 50 milliliters of water are added to the reaction mixture under reflux. An oil is separated which is isolated and dissolved in
milliliters of hot ethanol. Upon cooling, 47 milligrams of crystalline 2-phenoxy-5, 10-dimethyl-5, 10-dihydrophenazine are isolated for a 31% yield.
Example 13 Synthesis of 2,7-phenoxy-5,10-dimethyl-5,10-dihydrophenazine
2,7,7-Diphenoxy-5,10-dimethyl-5,10-dihydrofenazine is prepared from 2,7-dichlorophenazine. 2,7-Dichlorophenazine is prepared from the procedure described in synthesis example 3 for 2,7-bis (o-tolyl) phenazine. Diphenoxifenazine is produced by the reaction of dichlorophenazine with potassium phenolate in tetraglime. The resulting 2,7-diphenoxyphenazine, 0.35 grams, is refluxed in 100 milliliters of acetonitrile, 1.7 grams of sodium hydrosulfite, 0.53 grams of sodium carbonate, 3 milliliters of iodomethane and 0.1 grams of tetrabutylammonium acid sulfate. After refluxing for 3 days, 100 milliliters of water is added to the reaction slurry under reflux. The precipitated product is filtered off and recrystallized from ethanol. 210 milligrams of 2,7-diphenoxy-5,10-dimethyl-5,10-dihydrophenazine are isolated for a 55% yield.
Example 14 Synthesis of 1, 5, 10-trimethyl-2-phenyl-5, 10-dihydrophenazine
1, 5, 10-Trimethyl-2-phenyl-5,10-dihydrophenazine is produced in a 5-step process. The first stage involves a "coupling of Suzuki" reaction with 2-nitro-6-bromotoluene and phenylboronic acid. The procedure used is "Palladium Catalyzed Cross-Coupling Reactions of Arylboronic Acids with II-Deficient Heteroaryl Chlorides," Tetrahedron, 48, pp. 8117- 8126 (1992). This reaction is quantitative after 40 hours. 2-Nitro-6-phenyltoluene is isolated as an oil of the
"Suzuki link". It is then reduced to 2-amino-6-phenyltoluene with stannous chloride in concentrated HCl and methanol. The next stage is an aryl amination of type
Ullmann of the amine with 2-iodonitrobenzene. This reaction is carried out in nitrobenzene with copper as a catalyst. The product is isolated by distillation of the solvent followed by column chromatography. The resulting 2-nitrodiphenylamine is isolated as an impure oil and cyclized to l-methyl-2-phenylphenazine with iron powder. "Direct Ring Closure Through a Nitro Group I. Certain Aromatic Compounds with the Formation of Nitrogen Heterocycles: A New Reaction," by H. C. Waterman and D.L. They lived, J. Or. Chem., 14, 289-297 (1949).
The l-methyl-2-phenylphenazine is brought to a final reduction / alkylation stage as an oil. The oil is refluxed in 50 milliliters of acetonitrile, 1 milliliter of water, 0.9 grams of methyltributylammonium chloride, 2.1 grams of sodium carbonate, 8.7 grams of sodium hydrosulfite and 2 milliliters of iodomethane. After 16 hours, the reaction mixture is suspended by adding 50 milliliters of water to the reaction mixture under reflux. An oil is isolated which is isolated, then dissolved in ethyl acetate and washed with water. The ethyl acetate is removed and the oil is cleaned by column chromatography. Recrystallization from ethanol gives 88 milligrams of 1, 5, 10-trimethyl-2-phenyl-5,10-dihydrophenazine as an almost white solid.
Example 15 Synthesis of 2-phenyl-5,10-dimethyl-5,10-dihydrophenazine
2-Phenyl-5,10-dihydrophenazine is prepared in a 4-step process. The first stage involves the arilization of
4-bromo-3-nitrobiphenyl with aniline, in dimethylformamide. The resulting 2-nitro-4-phenyldiphenylamine is ring-closed to 2-phenylphenazine using sodium ethoxide and sodium borohydride by the procedure described in "A New Phenazine Synthesis, The Synthesis of Griseolutein Acid, Griseolutein A,
and Methyl Diacetyl Griseolutein B ", J. Chem. Soc., Chem, Commun., 1423-1425 (1970) 2-Phenylphenazine is reduced to 2-phenyl-5,10-dihydrophenazine by adding an aqueous solution of hydrosulfite to a solution of ethanol under reflux of phenazine.This dihydro product is isolated and then alkylated in a refluxing solution of acetonitrile containing iodomethane and sodium carbonate.The product is precipitated by the addition of water and is isolated. carbon and recrystallized from a mixture of acetone and ethanol to give a bright yellow crystalline solid.
Example 16 Synthesis of 2,7-diphenyl-5,10-dimethyl-5,10-dihydrophenazine
2, 7-Diphenyl-5,10-dimethyl-5,10-dihydrofenazine is prepared from 2,7-dichlorophenazine, 2,7-dichlorophenazine is prepared from the procedure described in Synthesis Example 3 for 2, 7. -bis (o-tolyl) phenazine. 2, 7-diphenylphenazine is made from the cross-coupling reaction of "Suzuki" with 2,7-dichlorophenazine and phenylboronic acid. Reference is made to the procedure described in "Palladium Catalyzed Cross-Coupling Reactions of Arylboronic Acids With Deficient Heteroarylchlorides," Tetrahedron, 48, p. 8117-8126.
660 milligrams of 2,7-diphenylphenazine are reduced and alkylated by refluxing in 10 milliliters of acetonitrile, 0.2 milliliters of water, 1 milliliter of iodomethane, 3.5 grams of sodium hydrosulfite, 0.21 grams of sodium carbonate and 60 milligrams of methyltributylammonium chloride. After 40 hours the reaction is suspended by dropping in 20 milliliters of water to the reaction suspension under reflux. 450 milligrams of 2,7-diphenyl-5,10-dimethyl-5,10-dihydrofenazine are isolated in a yield of 62.0%.
Example 17: Novel method for making 5, 10-dimethyl-5, 10-dihydrophenazine
, 10-Dimethyl-5, 10-dihydrofenazine can be easily made in a novel synthesis in a container starting with phenazine. In this synthesis, both reduction and alkylation proceed rapidly under moderate reaction conditions. Under a nitrogen atmosphere, they undergo reflux
650 grams of phenazine in 3.5 liters of acetonitrile with 100 milliliters of water, 899 milliliters of iodomethane (alkylating reagent), 765 grams of sodium carbonate powder (base), 723 grams of sodium hydrosulfite (reducing agent) and 130 grams of methyltributylammonium chloride (catalyst of
phase transfer) present. Phenazine is completely reduced and methylated after 5 hours. At this time, 4.5 liters of water is added to the reflux suspension for 25 minutes. Upon allowing to cool to room temperature, almost all 5, 10-dimethyl-5, 10-dihydrophenazine has precipitated. This is filtered off and redissolved in 1.95 liters of hot toluene. This toluene solution is filtered to remove inorganic salts. After filtration, 0.95 liters of toluene are removed by means of atmospheric distillation under nitrogen. The reaction is cooled to 85 ° C and 1 liter of ethanol is added for 20 minutes. The solution is gradually cooled to room temperature and maintained at room temperature for 4 hours before filtering. The resulting 5, 10-dimethyl-5, 10-dihydrophenazine is washed with 1 liter of water followed by 1 liter of cold ethanol. This product is subsequently dried to 650.2 grams of a white crystal for a yield of 85.3%.
Example 18 Synthesis of 1-methyl-1'-phenyl-4,4'-dipyridinium bis (hexafluorophosphate)
1-Phenyl-1-methyl-4,4'-dipyridinium bis (hexafluorophosphate) is prepared by first joining the phenyl group and
then the methyl group at 4,4'-dipyridyl. The phenyl group is linked using the procedure of Canadian Patent # 101346 entitled "Preparation of Bipyridinium Compounds" by Jhon G. Alien. The 4,4'-dipyridyl is quaternized with 2,4-dinitrochlorobenzene at 35 ° C; and only 1 equivalent to this temperature is used, which limits quaternization only to the 4,4'-dipyridyl side. The mono-accustomed intermediate is refluxed with 10 equivalents of iodomethane in acetonitrile to quaternize the remaining nitrogen. This reaction is completed after 1 hour with a yield of 97.6%. The mixed salt is dissolved in hot water, filtered and the product is separated by precipitation with the addition of a 1 molar solution of ammonium hexafluorophosphate.
Example 19 Synthesis of 1- (4-cyanophenyl) -1'-methyl-4,4'-bipyridinium bis (hexafluorophosphate)
Bis (hexafluorophosphate) of 1- (4-cyanophenyl) -1'-methyl-4,4'-bipyridinium is produced in a manner similar to bis (hexafluorophosphate) of 1-phenyl-1'-methyl-4,4'-dipyridinium in the synthesis example 18. The only difference is that 4-cyanoaniline is used to displace the group 2,4-
dinitrophenyl, instead of aniline. See Canadian Patent Number 1031346.
Example 20 Synthesis of 1- (4-methoxyphenyl) -1'-methyl-4,4'-dipyridinium bis (hexafluorophosphate)
Bis (hexafluorophosphate) of 1- (4-methoxyphenyl) -1 '-methyl-4,4'-dipyridinium similarly to bis (hexafluorophosphate) of 1-methyl-1'-phenyl-4,4'-dipyridinium is produced in the example of synthesis 18. The only difference is that para-anisidine is used to displace the 2,4-dinitrophenyl group, instead of aniline. See Canadian patent # 1031346.
Example 21 Synthesis of 1-phenyl-1 '- (4-dodecylphenyl) -4,4'-dipyridinium bis (hexafluorophosphate)
This viologen is made with reference to the patent
Canadian # 1031346. First quaternized 4,4 '-dipyridyl on one side at 35 ° C with 1 equivalent of 2,4-dinitrochlorobenzene. After displacement with dodecylaniline, the second nitrogen is quaternized with dinitrochlorobenzene. This quaternization is carried out with an excess of dinitrochlorobenzene
at reflux temperature. This dinitrophenyl group is then displaced with aniline to provide the dichloride salt of the desired product. The metathesis of hexafluorophosphate is carried out in hot MeOH with an acetonitrile solution of ammonium hexafluorophosphate.
Example 22 Synthesis of 1, 2, 6-trimethyl-1'-phenyl-4,4'-dipyridinium bis (tetrafluoroborate)
2, 6-Dimethyl-4,4'-dipyridyl is quaternized with a 5-fold excess of dinitrochlorobenzene at 50 ° C. The quaternization takes place with the unimpeded nitrogen to provide 2,6-dimethyl-1- (2,4-dinitrophenyl) -4,4'-dipyridinium chloride. This is reacted with aniline (see Canadian Patent # 1031346) to provide the 2,6-dimethyl-1'-phenyl-4,4'-dipyridinium chloride. Finally, the prevented nitrogen is quaternized with a 20-fold excess of iodomethane in refluxing acetonitrile. This quaternization is carried out after 1 hour and the resulting disubstituted dipyridinium salt is separated by filtration. This salt is dissolved in hot water and precipitated as the tetrafluoroborate salt with a 1 molar aqueous solution of sodium tetrafluoroborate.
Example 23 Synthesis of 1,1'-bis (2,6-dimethylphenyl) -4,4'-dipyridinium bis (tetrafluoroborate)
7.0 ml of 2,6-dimethylaniline are added to 40 ml of a 3: 2 solution of dimethylformamide / H20 and the mixture is heated under reflux under a nitrogen atmosphere. 5.0 g of 1,1'-bis (2,4-dinitrophenyl) -4,4'-dipyridinium are slowly added.
(salt of Cl ") in 50 ml of water (for 20 minutes) by means of a pressure equalizing addition funnel The black solution is refluxed for an additional 2.5 h, then cooled to produce an oily yellow precipitate The solid material is removed by filtration and discarded.The volume of the filtrate is reduced to ca. 10 ml by rotary evaporation.The addition of copious amounts of acetone produces a light brown solid which is redissolved in 10: 1 methanol / water.This solution is treated with activated charcoal to remove the color and is filtered, aqueous sodium tetrafluoroborate is added and the solution is allowed to stand at room temperature overnight. light brown color by vacuum filtration.
Example 24 Synthesis of 1,1'-bis (3,5-dimethylphenyl) -4,4'-dipyridinium bis (tetrafluoroborate)
6.7 ml of 3,5-dimethylaniline are added to 30 ml of a 3: 2 solution of dimethylformamide / H20 and the mixture is heated to reflux under a nitrogen atmosphere. 5.0 g of 1,1 '-bis (2,4-dinitrophenyl) -4,4'-dipyridinium (Cl salt ") in 50 ml of water (20 min) are added slowly by means of an addition funnel The black solution is refluxed for an additional 5 h, then cooled to produce a yellow-brown precipitate.The solid material is removed by filtration and discarded.The volume of the filtrate is reduced to ca. ml by rotary evaporation The addition of copious amounts of acetone yields an orange-brown solid which is redissolved in water, aqueous sodium tetrafluoroborate is added., which results in precipitation of the raw product as an orange solid. The product is first purified by digestion in ethanol, then by treatment with carbon for color removal in methanol / acetonitrile. After addition of water and removal of methanol and acetonitrile by rotary evaporation, the pure product is isolated as a chalky off-white solid by vacuum filtration.
Example 25 Synthesis of 1,1'-bis (2,4,6-trimethylphenyl) -4,4'-dipyridinium bis (tetrafluoroborate)
7.5 ml of 2,4,6-trimethylaniline are added to 40 ml of a 3: 2 solution of dimethylformamide / H20 and the mixture is heated to reflux under a nitrogen atmosphere. Slowly add 5.0 g of 1,1 '-bis (2,4-dinitrophenyl) -4,' -dipyridinium (Cl salt) in 50 ml of water (for 20 min) by means of an equal addition funnel The black solution is refluxed for an additional 6 h, then cooled to produce a yellow-brown precipitate.The solid material is removed by filtration and discarded.The volume of the filtrate is reduced to ca.10 ml By rotary evaporation, the addition of copious amounts of acetone produces a yellow-brown solid which is redissolved in 10: 1 methanol / water, aqueous sodium tetrafluoroborate is added, which causes a precipitate to form. bright yellow color The untreated solid is isolated by vacuum filtration and washed with small portions of cold methanol and water.The purification is obtained by treatment with carbon for color removal in methanol / acetonitrile.After the addition of water and removal of metal anol and acetonitrile by rotary evaporation, the pure product is isolated as a bright yellow solid by vacuum filtration.
Example 26 Synthesis of 1- (3,5-dimethoxyphenyl) -1'-methyl-4,4'-dipyridinium bis (hexafluorophosphate)
3.0 ml of 3,5-dimethoxyaniline is added to 25 ml of a 3: 2 solution of dimethylformamide / H20 and the mixture is heated to reflux under a nitrogen atmosphere. 3.0 g of (2,4-dinitrophenyl) -4,4'-dipyridinium (Cl salt ") in 50 ml of water are added slowly (over 20 min) by means of an addition funnel which equals the pressure. orange-coffee is refluxed for an additional 3 h, then cooled to produce a yellow precipitate.The solid material is removed by filtration and discarded.The volume of the filtrate is reduced to ca. 10 ml by rotary evaporation. copious amounts of acetone produce a light yellow solid, 0.30 g of this solid are dissolved in 80 ml of acetonitrile, together with an excess of methyl iodide, the solution is refluxed under a nitrogen atmosphere for 4 h and then Allows it to cool to room temperature The resulting precipitate is isolated as a bright orange solid by vacuum filtration.This untreated product (such as a mixture of Cl salts, "I") is redissolved in water. tetrafluoroborat or aqueous sodium and the solution is refrigerated overnight. The product
it is isolated as a yellow-orange solid by vacuum filtration. Purification is obtained by first redissolving in acetonitrile, and then precipitating as the chloride salt by adding a solution of tetraethylammonium chloride in acetone. The chloride salt is isolated by filtration and air-dried briefly. The product is then converted to the PF6 salt by dissolving with water, filtering and adding aqueous ammonium hexafluorophosphate to the filtrate.The resulting precipitate is isolated as a chalky off-white solid by vacuum filtration.The color of this compound is less yellow than the bis (hexafluorophosphate) of 1- (4-methoxyphenyl) -1'-methyl-4,4'-dipyridinium This has advantages in electrochromic devices when a residual yellow color is undesirable.
Example 27 Synthesis of 1-methyl- (2-methylphenyl) -4,4'-dipyridinium bis (hexafluorophosphate)
3.0 ml of o-toluidine are added to 25 ml of a 3: 2 solution of dimethylformamide / H20 and the mixture is heated under reflux under a nitrogen atmosphere. 3.0 g of 1- (2,4-dinitrophenyl) -4,4'-dipyridinium (Cl salt ") in 50 ml of water are added slowly (over 20 min) by means of a pressure equalizing addition funnel. orange-coffee solution
reflux for 3.5 additional hours, then cooled to produce a yellow precipitate. The solid material is removed by filtration and discarded. The volume of the filtrate is reduced to ca. 10 ml by rotary evaporation. The addition of copious amounts of acetone produces a light yellow solid which is redissolved in water. Aqueous ammonium hexafluorophosphate is added and the resulting white precipitate is isolated by vacuum filtration, washed with water and dried in a vacuum oven. Dissolve 0.70 g of this solid in 50 ml of acetonitrile, together with ca. 1.0 g of methyl iodide. The solution is refluxed under a nitrogen atmosphere for 6 h. The addition of dilute ammonium hexafluorophosphate, followed by the removal of acetonitrile by rotary evaporation, produces a clear tan solid.
Example 28 Synthesis of 1-methyl-1 '- (2, 4, 6-trimethylphenyl) -4,4'-dipyridinium bis (hexafluorophosphate)
The compound is prepared from 1- (2,4-dinitrophenyl) -4,4'-dipyridinium chloride (see Synthesis Example 18) by reaction with excess methyl iodide in refluxing acetonitrile. The 2,4-dinitrophenyl group is then displaced by reaction with 2,4,6-trimethylaniline in 1: 1 of
dimethylformamide / water (see Canadian Patent # 1031346). The untreated product is isolated as a mixed halide salt by reducing the volume of the reaction mixture to only a few ml, adding 200 ml of acetone and cooling overnight. The resulting solid is isolated by filtration, redissolved in water and precipitated as the hexafluorophosphate salt by the addition of aqueous ammonium hexafluorophosphate.
EXAMPLE 29 Preparation of novel salts of 2, 2 ', 6,6' -substituted-4, '-dipyridinium
The procedure described here for preparing compounds I-IV and VIII-XI is based on that established in: 1. (a) Minisci, Top, Curr. Chem., Vol. 62, (1976) pp. 1-48 (b) Synthesis, (1973) pp. 1-24 2. Minisci, Mondelli, Gardini and Porta, Tetrahedron, Vol. 28, (1972), 2403 3. Citterio, Minisci and Franchi, J. Or. Chem., Vol. 45, (1980), 4752 4. Anderson and Kochi, J. Am. Chem. Soc. , Vol. 92,
(1970), 1651
. Baltrop and Jackson, J. Chem. Soc., Perkin II, (1984), pp. 367-371
Preparation of 2- (2-phenylethyl) -4,4'-dipyridyl (I) and 2,2'-bis (2-phenylethyl) -4,4'-dipyridyl (II)
Procedure: To a stirring solution of 4,4'-dipyridyl (15.62 g, 0.1 mol) in a mixture of water (100 ml) and concentrated sulfuric acid (5.3 ml) is added hydroxycinnamic acid (32.0 g, 0.213 mol) and silver nitrate (1.7 g, 0.01 mole) and the mixture is heated to about 80 ° C while maintaining this temperature for 30 minutes, add ammonium peroxydisulfate (22.82 g, 0.1 mole) in small portions. After the addition, the mixture is maintained at the same temperature for an additional 2 hours. Subsequently, the reaction mixture is cooled to room temperature and neutralized with aqueous sodium hydroxide (10%). The resulting dark brown mixture is filtered and the filtrate is extracted several times with 25 ml portions of ethyl acetate. The organic layers are combined, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated to remove the solvent completely so that a viscous dark brown oil is left. From this oil mixture, the desired compounds I and II are isolated by
column chromatography on silica gel. The respective amounts of I and II that are obtained are 4.7 g and 1.76 g.
Preparation of 2- (3-phenyl (n-propyl)) -4,4'-dipyridyl (III) and 2,2'-bis (3-phenyl (n-propyl) -4,4'-dipyridyl (IV)
Procedure: Compounds III and IV are prepared by the same procedure described for the preparation of compounds I and II except that 4-phenylbutyric acid is used in place of hydroxycinnamic acid. The respective amounts of III and IV that are obtained are 3.3 g and 2.15 g.
Preparation of: 2, 2 ', 6-trimethyl-6' - (2-phenylethyl) -4,4'-dipyridyl (V); 2, 2'-dimethyl-6,6 '-bis (2-phenylethyl) -4,' dipyridyl (VI) and 2-methyl-2 ', 6,6' -tris (2-phenylethyl) -4,4 ' dipyridyl (VII)
Procedure: To a stirred suspension of sodium amide (29.2 g, 0.75 mol) in m-xylene (80 ml) is added 2, 2 ', 6,6'-tetramethylpyridyl (5.3 g, 0.025 mol) under an argon atmosphere . After brief agitation, benzyl chloride (50 g, 0.39 mol) is added slowly over a period of 15-30 minutes and the mixture is refluxed for 15-20 hours. After this time the heating is stopped, the reaction mixture is cooled to temperature
environment and cold water (5-10 ml) is added with caution to destroy the unreacted sodium amide. The mixture is acidified with concentrated hydrochloric acid and then extracted with methylene chloride several times., with 25 ml portions. This operation helps remove the unreacted benzyl chloride and the m-xylene solvent. The organic layer is separated and discarded. The aqueous solution is now made basic with sodium hydroxide (20% aqueous solution) and the mixture is extracted 2-3 times with 25 ml portions of methylene chloride. The organic layers are combined, dried over anhydrous magnesium sulfate and filtered. Filtration by complete evaporation of the solvent gives a viscous brown oil (9.2 g). The desired compounds V, VI and VII are isolated from the mixture by silica gel column chromatography.
Preparation of 2, 2 ', 6-trimethyl-6'-n-hexyl-4,4'-dipyridyl (VIII) and 2,2'-dimethyl-6,6' -bis (n-hexyl) -4,4 '-dipyridyl (IX):
Procedure: To a magnetically stirred solution of 2,2 ', 6,6'-tetramethyl-4,4'-dipyridyl (5.3 g, 0.025 mol) in pure tetrahydrofuran (80 ml) cooled to -78 ° C (dry ice and 2-propanol) is added under an argon atmosphere a solution of cyclohexane (2.0 M) of n-butyllithium (1.76 g, 0.0275 moles) from a dropping funnel over a period of 20 minutes. The solution turns dark blue immediately. HE
Allow the mixture to warm to -30 ° C for 5 minutes and then cool again to -78 ° C. A solution of 1-chloropent no (2.93 g, 0.0275 mol) in pure tetrahydrofuran (15 ml) is now added from a dropping funnel over a period of 10 minutes. After the addition, the color mixture turns dark purple. After stirring at -78 ° C for a short period, the mixture is allowed to warm to room temperature. Pure water (2-3 ml) is added cautiously to destroy any butyllithium that has not reacted and is still present, and the mixture is diluted with more pure water (100 ml) and extracted 2-3 times with portions of water. 25 ml of ethyl acetate. The organic layers are combined, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated to remove the solvent completely. This provides 7.2 g of a yellow-brown oil. Compounds VIII and IX are isolated from the oil by column chromatography on silica gel, as solid products.
Preparation of 2,2 '-6-trimethyl-6' - (3-phenyl (n-propyl)) -4,4'-dipyridyl (IX) and 2,2 '-dimethyl-6,6' -bis (3 -phenyl (n-propyl)) -4,4'-dipyridyl (X):
Procedure: Compounds X and XI are prepared in the same manner as described for the preparation in compounds VIII
and IX, except for the use of l-bromo-2-phenylethane in place of 1-chloropentane as the alkylating agent.
Conversion of compounds I to XI to their respective 1, 1'-dimethyl-4,4'-dipyridinium diiodide salts:
The diiodide salts of compounds I to X are prepared by refluxing each of these with an equivalent molar excess of iodomethane in pure acetonitrile for 24 to 48 hours, and the resulting quaternary salts are filtered, washed thoroughly with fresh acetonitrile , followed by wetting with dry acetone.
Conversion of compounds I-IV, VIII and IX to their respective bis (hexafluorophosphate) 1,4-dimethyl-4,4'-dipyridinium salts:
Typical procedure: The diiodide salt (5 moles) prepared as described above is dissolved in pure water (100-150 ml) and the solution is stirred with charcoal for color removal (1.0 g) for 2-3 hours at room temperature. The suspension is filtered and the colorless filtrate is treated with an aqueous solution of 1 molar ammonium hexafluorophosphate until precipitation is complete. After allowing to stand for 1 hour, the precipitate is filtered with suction, washed with pure water
(20 ml) 2-3 times and recrystallized from water to obtain the pure salt. Yields vary with individual compounds between 20-80%.
Conversion of compound VI to the diperchlorate salt of 1,1'-dimethyl-4,4'-dipyridinium:
The diiodide salt of compound IV as prepared above is first dissolved in hot pure water (100 ml) and an aqueous solution (5%) of sodium perchlorate is added to the solution until precipitation is complete. The precipitate is filtered, washed 4-5 times with pure water (25 ml) and the wet precipitate is recrystallized and purified by treatment with carbon for color removal in a mixture (8: 2 v / v) of acetonitrile and water. The yield of the yellow solid is 32%.
Conversion of compound VII and VIII to the bis (tetrafluoroborate) 1,1'-dimethyl-4,4'-dipyridinium salt:
The diiodide salt (2.0 g, 3.5 mmol) is dissolved in pure water (25 ml) at room temperature. The solution is treated with charcoal for color removal, and to the colorless filtrate is added an aqueous solution of sodium tetrafluoroborate (2 molar) until the precipitation is complete. He
The resulting light yellow precipitate is filtered, washed 4-5 times with 25 ml portions of pure water. The solid precipitate is then recrystallized from hot water to obtain a colorless solid.
Example 30 Electrochromic device green / blue
Symmetrically substituted aryl viologens are prepared from the reaction of the appropriate aniline derivative with 1,1'-bis (2,4-dinitrophenyl) -4,4'-dipyridinium as previously described in Examples 23 and 24. Ferrocene is commercially obtained (Aldrich) and purified by sublimation before use. Two concentrated solutions are prepared in separate small bottles, one contains 60 mM ferrocene in propylene carbonate and the second contains 30 mM each of 1, 1 '-bis (2,4,6-trimethylphenyl) bis (tetrafluoroborate) - 4, '-dipyridinium and bis (tetrafluoroborate) of 1,1' -diphenyl-4,4'-dipyridinium in propylene carbonate. Both concentrated solutions are deoxygenated with dry nitrogen. Equal volumes of each concentrated solution are introduced into a clean bottle to produce a mixture which has approximately 30 mM of ferrocene and 15 mM of each of the two derivatives of
viologen This multiple component mixture is then used to fill electrochromic devices. The electrochromic window devices are manufactured as is known in the art with TEC-20 glass from Libbey-Owens-Ford with a cell separation of 137 micrometers. The devices are approximately 30.5 x 5.1 cm (l1 X 2") in area and when they are filled by inserting them into the solution described earlier in the device through one of the two holes drilled in the top plate, both holes are plugged using a hot glue gun The application of 1.2 V through this electrochromic device results in a uniform coloration in a green / blue state, however, a certain graduation is observed (through an intermediate green) both in the coloration and in the the cleared.
Example 31 Gray electrochromic device
Two concentrated solutions are prepared in separate small bottles, one contains 60 mM ferrocene in propylene carbonate and the second contains 30 mM each of 1, 1 '-bis (2,4,6-trimethylphenyl) bis (tetrafluoroborate) - 4, 4 '-dipyridinium in propylene carbonate. Both solutions
concentrated are deoxygenated with dry nitrogen. Equal volumes of each concentrated solution are placed in a clean bottle to produce a mixture which is approximately 30 mM in ferrocene and 15 mM in each of the two viologen derivatives. This mixture of multiple components is then used to fill electrochromic devices. Electrochromic window devices are manufactured as is known in the art, with TEC-20 glass from Libbey-Owens-Ford with a cell separation of 137 micrometers. The devices have an area of approximately 30.5 cm (1 'X 2") in area and when they are filled by introducing them into the solution described above in the device through one of the two holes drilled in the upper plate. They are covered using a hot glue gun.The application of 1.2 V through this electrochromic device results in a uniform coloration in a dark blue / green (moderately gray) state.No graduation is observed during staining or lightening.
Example 32 Electrochromic devices having colors ranging from green / gray to blue / gray green
Three concentrated solutions, one containing 60 mM ferrocene in propylene carbonate, one containing bis (tetrafluoroborate) of 1,1 '-bis (2,4,6-trimethylphenyl) -4,4' - are prepared in small separate vials. 60 mM dipiridinium (VI) in propylene carbonate and one containing bis (tetrafluoroborate) of 1, 1 '-bis (3,5-dimethylphenyl) -4,4' -dipyridinium (V2) 60 mM in propylene carbonate. The three concentrated solutions are deoxygenated with dry nitrogen. Aliquots of each of the concentrated solutions are introduced into 5 clean jars in such a way that the following solutions are produced:
A) ferrocene 30 mM / 15 mV VI p / 15 mM V2 B) ferrocene 30 mM / 18 mV VI p / 12 mM V2 C) ferrocene 30 mM / 20 mV VI p / 10 mM V2 D) ferrocene 30 mM / 21 mV VI p / 9 mM V2 E) ferrocene 30 mM / 24 mV VI p / 6 mM V2
These mixtures of multiple components are then used to fill electrochromic devices. The electrochromic window devices are manufactured as is known in the art with TEC-20 glass from
Libbey-Owens-Ford with a cell separation of 137 micrometers. The devices have an area of approximately 30.5 cm x 5.1 cm (! 'X 2") in area and when filled to
Insert them into the solution described above in the device through one of the two holes drilled in the upper plate. Both holes are then plugged using a hot glue gun. The application of 1.2 V through each of these electrochromic devices results in a uniform coloration, with the exact color when the total darkness varies uniformly from green-gray for device A to blue-green gray for device E. It is observed slight graduation during the coloring of A, B and C, while D and E do not show appreciable graduation during coloration or clearance.
Example 33 Gray electrochromic devices
A solution consisting of 25 mM 1, 1-dimethyl ferrocene, 100 mM 2-hydroxy-4-methoxybenzophenone (as a UV stabilizer), 1,1'-bis bis (tetrafluoroborate) (2,6-dimethyl) f eni 1) - 4, 4 '- 18 mM dipyridinium, bis (tetrafluoroborate) of 1, 1' -bis (3, 5-dimethylphenyl) -4,4 '-dipyridinium, 12 mM and 3% (w / w) Polymethylmethacrylate in propylene carbonate is deoxygenated with dry nitrogen. Electrochromic window devices are manufactured as is known in the art with TEC-20 glass from Libbey-Owens-
Ford with a cell separation of 137 micrometers. Similarly, electrochromic mirrors are manufactured using a transparent TEC-20 front plate with either a TEC-20 back plate which has previously been covered with silver on one side opposite the conductive coating (fourth reflective surface) or has been coated with another reflecting metal (third reflecting surface). These devices measure approximately 5.1 cm x 13 cm (2"X 5") and are filled with the electrochromic solution described above by means of a vacuum re-polishing technique. The vacuum filling holes of the devices are covered with a UV curing material. After four months, the representative L * a * b * values (A / 2 degrees) are as follows:
initial darkened
L * a * b * L * a * b * fourth reflecting surface 87.51 - 1.42 + 12.60 32.96 -0.37 -6.27 third reflecting surface 78.17 +0.07 + 10.21 30.44 -5.12 -3.68
Example 34 Gray electrochromic device
An electrochromic device is prepared from two pieces of TEC 15 glass separated 137 micrometers by an epoxy perimeter seal. The device is filled with a nitrogen purged propylene carbonate solution of 14 mM 5,10-diisopropyl-5,10-dihydrophenazine, 5, 10-dimethyl-5,10-dihydrobenzo (A, C) phenazine, 14 mM, and bis (tetrafluoroborate) of bis (3,5-dimethylphenyl) -4,4'-dipyridinium 34 mM. In transparent state, the device is slightly yellow and when 0.8 volts are applied, the device is a very dark gray color. From the transparent state spectrum, it is found that the color coordinates (A / 2 degrees) L *, a *, b * are equal to 89.19, -0.27, 10.7 and 0.8 volts L *, a *, b * are equal to 17.72, 9.03 and 7.37. The CIÉ curve of transmittances with white light was 75% transparent and 2.5% darkened at 0.8 volts. Not only will the device be gray when activated, but it would remain remarkably low in transmission when it was completely dark. Although the invention has been described in detail herein in accordance with certain preferred embodiments thereof, many modifications and changes thereto can be made by those familiar with the art without departing from the spirit of the invention. Accordingly, it is our objective to be limited only by the scope of the appended claims and not by the details and
instrumentalities described in the modalities shown here. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects or products to which it refers.
Claims (111)
1. An electrochromic device, characterized in that it comprises: separate front and rear elements, having front and rear surfaces; a layer of transparent conductive material placed on the rear surface of the front element and the front surface of the rear element, and a sealed perimeter member joining the separated front and rear elements in a separate relation to define a chamber therebetween, in where the chamber contains an electrochromic medium, the electrochromic medium comprises at least three electroactive materials, at least two of which are electrochromic, wherein the medium generally maintains a preselected color perceived through the normal voltage range of the electrochromic device.
2. The electrochromic device according to claim 1, characterized in that the concentrations of at least three electroactive materials are chosen to produce a preselected perceived color.
3. The electrochromic device according to claim 1, characterized in that the electrochromic device does not show graduation.
The electrochromic device according to claim 1, characterized in that at least two electrochromic materials include at least one electrochemically reducible material and at least one electrochemically oxidizable material.
5. The electrochromic device according to claim 1, characterized in that at least two electrochromic materials are both electrochemically reducible materials or both electrochemically oxidizable materials.
The electrochromic device according to claim 1, characterized in that one of the electrochromic materials is selected from the group consisting of: confined on the surface and electrodeposition.
The electrochromic device according to claim 1, characterized in that all of the electroactive materials are in phase in solution.
8. The electrochromic device according to claim 7, characterized in that the redox potentials of all the electroactive materials that are Anodic are within approximately 200 mV other, and wherein the redox potentials of all the electroactive materials that are cathode are within approximately 200 mV of other.
9. The electrochromic device according to claim 8, characterized in that the redox potentials of all the electroactive materials that are anodic are within 60 mV other, and where the redox potentials is the totality of the electroactive materials that are Cathodics are within 60 mV other.
The electrochromic device according to claim 9, characterized in that the redox potentials of all the electroactive materials that are anodic are within 40 mV other, and wherein the redox potentials of all the electroactive materials that are cathode are within 40 mV between them.
11. The electrochromic device according to claim 10, characterized in that the electrochromic device does not show graduation.
The electrochromic device according to claim 1, characterized in that the redox potentials of all the electroactive materials which are anodic are within approximately 200 mV other, and wherein the Redox potentials of all electroactive materials that are cathode are within approximately 200 mV other.
The electrochromic device according to claim 12, characterized in that the redox potentials of all the electroactive materials that are anodic are within 60 mV other, and where the redox potentials of all the electroactive materials that are cathode are within 60 mV each other.
14. The electrochromic device according to claim 13, characterized in that the redox potentials of all the electroactive materials that are anodic are within 40 mV each other, and wherein the redox potentials of all the electroactive materials that are cathode are within 40 mV each other.
The electrochromic device according to claim 1, characterized in that at least three electroactive species include at least one cathodic material that is selected from the group consisting of salts of: 1,1'-diphenyl-4,4 '- dipyridinium, 1,1'-bis (2,6-dimethylphenyl) -4,4'-dipyridinium; 1,1 '-bis (3,5-dimethylphenyl) -4,4'-dipyridinium; 1-phenyl-1 '- (4-dodecylphenyl) -4,4'-dipyridinium; 1,1'-bis (2,4,6-trimethylphenyl) -4,4'-dipyridinium; 1- (3,5-dimethoxyphenyl) -1'-methyl-4,4'-dipyridinium; 1-methyl-1'-phenyl-4,4'-dipyridinium; 1-methyl-1 '- (2-methylphenyl) -4,4'-dipyridinium 1-methyl-1' - (2-methylphenyl) -4,4'-dipyridinium; 1- (4-methoxyphenyl) -1 '-methyl-4, 4' - dipyridinium; 1-methyl-1 '- (2,, 6-trimethylphenyl) -4,4'-dipyridinium; 1,2,6-trimethyl-1'-phenyl-4,4'-dipyridinium; 1,1'-dimethyl-2,6-diphenyl-4, '-dipyridinium; 1,1'-bis (3-phenyl (n-propyl)) -4,4'-dipyridinium; 1,1 '-dimethyl-4,4'-dipyridinium; 1,1'-dimethyl-2- (3-phenyl (n-propyl)) -4,4'-dipyridinium; 1,1 '-dimethyl-4,4' - (1, 3, 5-triazine-2,4-diyl) dipyridinium; 1,1'-dibenzyl-2, 2 ', 6,6' -tetramethyl-4,4'-dipyridinium; 1,1'-ethylene-4,4'-dimethyl-2, 2'-dipyridinium; and 1,1 '-dimethyl-2, 2'-bis (3-phenyl (n-propyl)) -4,4'-dipyridinium and wherein at least three electroactive species include at least one anodic material that is selected of the group consisting of: N, N, N ', N' -tetramethyl-p-phenylenediamine; 2,5, 10-trimethyl-3-phenyl-5,10-dihydrophenazine; 5-ethyl-10-methyl-5,10-dihydrofenazine; 5, 10-dimethyl-5, 10-dihydrobenzo (A) phenazine; 2,7-diphenoxy-5,10-dimethyl-5,10-dihydrophenazine; 2-phenoxy-5, 10-dimethyl-5,10-dihydrophenazine; 2, 7-bis (o-tolyl) -5,10-dimethyl-5,10-dihydrophenazine; 2,3-dimethyl-7-trifluoromethyl-5,10-diethyl-5,10-dihydrophenazine; 5, 10-dimethyl-5,10-dihydrophenazine; 2, 3-diphenyl-5,10-dimethyl-5,10-dihydrofenazine; 2,7-diphenyl-5,10-dimethyl-5,10-dihydrophenazine; 2-vinyl-5, 10-dimethyl-5,10-dihydrophenazine; 2-phenyl-5,10-dimethyl-5,10-dihydrophenazine; 5,10-diisopropyl-5,10-dihydrophenazine; 5, 10-dimethyl-5,10-dihydrodibenzo (A, C) phenazine; 1,5, 10-trimethyl-2-phenyl-5,10-dihydrophenazine; 2,3,5,10-tetramethyl-7-trifluoromethyl-5,10-dihydrophenazine and 2,3,5,10-tetramethyl-5,10-dihydrobenzo (B) phenazine.
16. The electrochromic device according to claim 1, characterized in that at least three electroactive species include about 17 millimolar of 5,10-dimethyl-5,10-dihydrophenazine, about 8.5 millimolar of 2-phenyl-5,10-dimethyl-5 , 10-dihydrophenazine, approximately 4.3 millimolar of 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 17 millimolar of bis (tetrafluoroborate) of 1,1'-dibenzyl-2, 2 ', 6, 6'-tetramethyl-4,4 '-dipyridinium and approximately 17 _ millimolar of bis (hexafluorophosphate) of 1,1'-ethylene-4,4'-dimethyl-2,2'-dipyridinium.
The electrochromic device according to claim 1, characterized in that at least three electroactive species include approximately 17 millimolar of 5,10-dimethyl-5,10-dihydrofenazine, approximately 8.5 millimolar of 2-phenyl-5,10-dimethyl. -5,10-dihydrofenazine, approximately 4.3 millimolar of 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 19 millimolar of bis (tetrafluoroborate) of 1,1'-dibenzyl-2, 2 ', 6,6'-tetramethyl-4,4'-dipyridinium and approximately 15 millimolar of bis (hexafluorophosphate) of 1,1'-ethylene-4,4'-dimethyl-2,2'-dipyridinium.
18. The electrochromic device according to claim 1, characterized in that the perceived color Preselected is a member of the group consisting of red, yellow, green, blue, purple and gray.
19. The electrochromic device according to claim 18, characterized in that the pre-selected color is gray.
The electrochromic device according to claim 19, characterized in that at least one of the electroactive materials includes a 5,10-dialkyl-5,10-dihydrophenazine wherein at least one of the 2, 3, 7 and 7 positions 8 contains a member of the group consisting of: phenyl; substituted phenyl; vinyl and phenoxy.
The electrochromic device according to claim 19, characterized in that at least one of the electroactive materials includes an electrochromic material that is selected from the group consisting of salts of: 1, 1 '-diphenyl-4,4'-dipyridinium , 1, 1'-bis (2,6-dimethylphenyl) -4,4'-dipyridinium; 1,1'-bis (3,5-dimethylphenyl) -4,4'-dipyridinium; 1-phenyl-l '- (4-dodecylphenyl) -4,4'-dipyridinium; 1, l'-bis (2,4,6-trimethylphenyl) -4,4'-dipyridinium; 1- (3,5-dimethoxyphenyl) -1 '-methyl-4,' -dipyridinium; 1-methyl-1'-phenyl-4,4'-dipyridinium; . 1-methyl-l '- (2-methylphenyl) -4,4'-dipyridinium 1- (4-methoxyphenyl) -1'-methyl-4,4'-dipyridinium; 1-methyl-1 '- (2,4,6-trimethylphenyl) -4,4'-dipyridinium; 1,2,6-trimethyl-1'-phenyl-4,4'-dipyridinium; 1,1 '-dimethyl-2,6-diphenyl-4,4'-dipyridinium; 1,1'-bis (3-phenyl (n-propyl)) -4,4'-dipyridinium; 1, 1 '-dimethyl-4, 4' - dipyridinium; 1,1'-dimethyl-2- (3-phenyl (n-propyl)) -4,4'-dipyridinium; 1,1'-dimethyl-4,4 '- (1, 3,5-triazine-2,4-diyl) dipyridinium; 1,1'-dibenzyl-2, 2 ', 6,6'-tetramethyl-4,4'-dipyridinium; 1,1'-ethylene-4,4'-dimethyl-2, 2'-dipyridinium; and 1,1 '-dimethyl-2, 2'-bis (3-phenyl (n-propyl)) -4,4'-dipyridinium.
22. The electrochromic device according to claim 19, characterized in that the device maintains a transmittance spectrum that results in color coordinates, A / 2 degrees, so that C * is between zero and approximately 22.
23. The electrochromic device according to claim 22, characterized in that the device maintains a transmittance spectrum that results in color coordinates, A / 2 degrees, so that a * is between zero and approximately -18.
24. The electrochromic device according to any of claims 1 to 23, characterized in that the electrochromic device is a member of the group consisting of: an electrochromic window, a display device and a motor vehicle sunroof.
25. An electrochromic device, characterized in that it comprises: separate front and rear elements, each having front and rear surfaces; a layer of transparent conductive material placed on the rear surface of the front element and the front surface of the rear element, and a perimeter sealing member joining the separate front and rear elements together, in a separate relation to define a chamber therebetween where the chamber contains an electrochromic medium, the electrochromic medium comprises at least three electroactive materials, at least two of which are electrochromic, wherein the redox potentials of all the electroactive materials that are anodic are between approximately 200 mV between yes, and where the redox potentials of all the electroactive materials that are cathode are within approximately 200 mV each other.
26. The electrochromic device according to claim 25, characterized in that the redox potentials of all of the electroactive materials that are anodic are between 60 mV each other, and wherein the redox potentials of all the electroactive materials that are cathode are within of 60 mV each other.
27. The electrochromic device according to claim 26, characterized in that the redox potentials of all the electroactive materials that are anodic are within 40 mV each other, and wherein the potentials Redox of all the electroactive materials that are cathode are within 40 mV each other.
The electrochromic device according to claim 25, characterized in that at least three electroactive species include at least one cathodic material that is selected from the group consisting of salts of: 1,1'-diphenyl-4,4 '- dipyridinium, 1,1'-bis (2,6-dimethylphenyl) -4,4'-dipyridinium; 1,1 '-bis (3,5-dimethylphenyl) -4,4'-dipyridinium; 1-phenyl-1 - (4-dodecylphenyl) -4,4'-dipyridinium; 1,1'-bis (2,4,6-trimethylphenyl) -4,4'-dipyridinium; 1- (3,5-dimethoxyphenyl) -1'-methyl-4,4'-dipyridinium; 1-methyl-1'-phenyl-4,4'-dipyridinium; 1-methyl-1 '- (2-methylphenyl) -4,4'-dipyridinium 1- (4-methoxyphenyl) -1' -methyl-4,4 '-dipyridinium; 1-methyl-1 '- (2,4,6-trimethylphenyl) -4,4'-dipyridinium; 1, 2, 6-trimethyl-1'-phenyl-4,4'-dipyridinium; 1,1'-dimethyl-2,6-diphenyl-4, '-dipyridinium; 1,1 '-bis (3-phenyl (n-propyl)) -4,4'-dipyridinium; 1,1'-dimethyl-4,4'-dipyridinium; 1,1'-dimethyl-2- (3-phenyl (n-propyl)) -4,4'-dipyridinium; 1,1'-dimethyl-4,4 '- (1, 3, 5-triazine-2,4-diyl) dipyridinium; 1,1'-dibenzyl-2, 2 ', 6,6'-tetramethyl-4,4'-dipyridinium; 1, 1-ethylene-4,4'-dimethyl-2, 2'-dipyridinium; and 1,1 '-dimethyl-2,2' -bis (3-phenyl (n-propyl)) -4,4'-dipyridinium and wherein at least three electroactive species include at least one anode material that is selected of the group consisting of: N, N, N ', N' -tetramethyl-p-phenylenediamine; 2,5, 10-trimethyl-3-phenyl-5,10-dihydrophenazine; 5-ethyl-10-methyl-5,10-dihydrofenazine; 5, 10 -dimethyl-5, 10- dihydrobenzo (A) phenazine; 2,7-diphenoxy-5,10-dimethyl-5,10-dihydrophenazine; 2-phenoxy-5, 10-dimethyl-5,10-dihydrophenazine; 2, 7-bis (o-tolyl) -5,10-dimethyl-5,10-dihydrofenazine; 2,3-dimethyl-7-trifluoromethyl-5,10-diethyl-5,10-dihydrophenazine; 5, 10-dimethyl-5,10-dihydrophenazine; 2, 3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine; 2,7-diphenyl-5,10-dimethyl-5,10-dihydrofenazine; 2-vinyl-5, 10-dimethyl-5,10-dihydrophenazine; 2-phenyl-5,10-dimethyl-5,10-dihydrophenazine; 5,10-diisopropyl-5,10-dihydrophenazine; 5, 10-dimethyl-5,10-dihydrodibenzo (A, C) phenazine; 1, 5, 10-trimethyl-2-phenyl-5,10-dihydrophenazine; 2,3,5,10-tetramethyl-7-trifluoromethyl-5,10-dihydrofenazine and 2,3,5,10-tetramethyl-5,10-dihydrobenzo (B) phenazine.
29. The electrochromic device according to claim 25, characterized in that at least three electroactive species include about 17 millimolar of 5,10-dimethyl-5,10-dihydrofenazine, about 8.5 millimolar of 2-phenyl-5,10-dimethyl. -5,10-dihydrophenazine, about 4.3 millimolar of 2,3-diphenyl-5,10-dimethyl-5,10-dihydrofenazine, about 17 millimolar of 1,1'-dibenzyl-2,2'-bis (tetrafluoroborate), 6,6 '-tetramethyl-4,4'-dipyridinium and approximately 17 millimolar of bis (hexafluorophosphate) of 1,1'-ethylene-4,4'-dimethyl-2,2'-dipyridinium.
30. The electrochromic device according to claim 25, characterized in that at least three electroactive species include about 17 millimolar of 5,10-dimethyl-5,10-dihydrophenazine ", about 8.5 millimolar of 2-phenyl-5,10-dimethyl-5,10-dihydrofenazine, about 4.3 millimolar of 2,3-diphenyl- 5, 10-dimethyl-5,10-dihydrofenazine, approximately 19 millimolar of 1,1'-dibenzyl-2, 2 ', 6,6' -tetramethyl-4,4'-dipyridinium bis (tetrafluoroborate) and approximately 15 millimolar of bis (hexafluorophosphate) of 1,1 '-ethylene-4,4'-dimethyl-2,2'-dipyridinium
31. The electrochromic device according to claim 25, characterized in that the preselected perceived color is a member of the group. which consists of red, yellow, green, blue, purple and gray
32. The electrochromic device according to claim 31, characterized in that the preselected color is gray
33. The electrochromic device according to claim 32, characterized in that at least one of the electro materials active includes a 5,10-dialkyl-5,10-dihydrofenazine wherein at least one of positions 2, 3, 7 and 8 contains a member of the group consisting of: phenyl; substituted phenyl; vinyl and phenoxy.
34. The electrochromic device according to claim 33, characterized in that at least one of the electroactive materials includes a material cathodic electrochromic which is selected from the group consisting of salts of: 1, 1 '-diphenyl-4,4'-dipyridinium, 1,1'-bis (2,6-dimethylphenyl) -4,4'-dipyridinium; 1, l'-bis (3,5-dimethylphenyl) -4,4'-dipyridinium; 1-phenyl-1 '- (4-dodecylphenyl) -4,4'-dipyridinium; 1,1 '-bis (2,4,6-trimethylphenyl) -4,4'-dipyridinium; 1- (3,5-dimethoxyphenyl) -1'-methyl-4,4'-dipyridinium; 1-methyl-1'-phenyl-4,4'-dipyridinium; 1-methyl-l '- (2-methylphenyl) -4,4'-dipyridinium 1- (4-methoxyphenyl) -1'-methyl-4,4' -dipyridinium; l-methyl-1 '- (2,4,6-trimethylphenyl) -4,4'-dipyridinium; 1,2,6-trimethyl-1'-phenyl-4,4'-dipyridinium; 1,1'-dimethyl-2,6-diphenyl-4,4'-dipyridinium; 1,1'-bis (3-phenyl (n-propyl)) -4,4'-dipyridinium; 1,1'-dimethyl-4,4'-dipyridinium; 1,1'-dimethyl-2- (3-phenyl (n-propyl)) -4,4'-dipyridinium; 1,1'-dimethyl-4,4 '- (1, 3, 5-triazine-2,4-diyl) dipyridinium; 1,1'-dibenzyl-2, 2 ', 6,6' -tetramethyl-4,4'-dipyridinium; 1,1 '-ethylene-4,4'-dimethyl-2, 2'-dipyridinium; and 1,1'-dimethyl-2,2'-bis (3-phenyl (n-propyl)) -4,4'-dipyridinium.
35. The electrochromic device according to claim 32, characterized in that the device maintains a transmittance spectrum that results in color coordinates, A / 2 degrees, so that C * is between zero and approximately 22.
36. The electrochromic device according to claim 35, characterized in that the device maintains a transmittance spectrum that results in color coordinates, A / 2 degrees, so that a * is between zero and approximately -18.
37. The electrochromic device according to claim 25, characterized in that the electrochromic device is a member of the group consisting of: an electrochromic window, a display device and a motor vehicle sunroof.
38. An electrochromic mirror of variable reflectance for automobile vehicles, characterized in that it comprises: separate front and rear elements, each having front and rear surfaces; a layer of transparent conductive material placed on the rear surface of the front element; a reflector placed on one side of the rear element with the proviso that, if the reflector is on the rear surface of the rear element, then the front surface of the rear element contains a layer of transparent conductive material; and a perimeter sealing member joining the separate front and rear elements together, in a separate relationship to define a chamber therebetween; wherein the chamber contains an electrochromic medium, the electrochromic means comprises at least three electroactive materials, at least two of which are electrochromic, wherein the medium generally maintains a perceived color preselected through the normal mounting range of the electrochromic mirror.
39. The electrochromic mirror according to claim 38, characterized in that the concentrations of at least three electroactive materials are chosen to produce a preselected perceived color.
40. The electrochromic mirror according to claim 38, characterized in that the electrochromic mirror does not show graduation.
41. The electrochromic mirror according to claim 38, characterized in that at least two electrochromic materials include at least one electrochemically reducible material and at least one electrochemically oxidizable material.
42. The electrochromic mirror according to claim 41, characterized in that the electrochromic means further comprises at least one additional electroactive material that is selected from the group consisting of anodic electrochromic materials and cathode electrochromic materials.
43. The electrochromic mirror according to claim 38, characterized in that one of the electrochromic materials is selected from the group consisting of: confined on the surface and electrodeposition.
44. The electrochromic mirror according to claim 38, characterized in that the electroactive materials are in phase in solution.
45. The electrochromic mirror according to claim 44, characterized in that the redox potentials of all the electroactive materials that are anodic are within approximately 200 mV each other, and wherein the redox potentials of all the electroactive materials that are cathode are within of approximately 200 mV each other.
46. The electrochromic mirror according to claim 45, characterized in that the redox potentials of all the electroactive materials that are anodic are within about 60 mV each other, and wherein the redox potentials of all the electroactive materials that are cathode are within of approximately 60 mV each other.
47. The electrochromic mirror according to claim 46, characterized in that the redox potentials of all the electroactive materials that are anodic are within approximately 40 mV each other, and wherein the redox potentials of all the electroactive materials that are cathode are within of approximately 40 mV each other.
48. The electrochromic mirror according to claim 47, characterized in that the electrochromic mirror does not show graduation.
49. The electrochromic mirror according to claim 38, characterized in that the redox potentials of all electroactive materials that are anodic are within approximately 200 mV each other, and wherein the redox potentials of all the electroactive materials that are cathode are within approximately 200 mV of each other.
50. The electrochromic mirror according to claim 49, characterized in that the redox potentials of all the electroactive materials that are anodic are within about 60 mV each other, and wherein the redox potentials of all the electroactive materials that are cathode are within of approximately 60 mV each other.
51. The electrochromic mirror according to claim 50, characterized in that the redox potentials of all the electroactive materials that are anodic are within approximately 40 mV each other, and wherein the redox potentials of all the electroactive materials that are cathode are within of approximately 40 mV each other.
52. The electrochromic mirror according to claim 38, characterized in that at least three electroactive species include at least one cathodic material that is selected from the group consisting of salts of: 1,1 '-diphenyl-4,4' - dipyridinium, 1,1'-bis (2,6-dimethylphenyl) -4,4'-dipyridinium; 1,1 '-bis (3,5-dimethylphenyl) -4,4'-dipyridinium; 1-phenyl-1 '- (4-dodecylphenyl) -4,4'-dipyridinium; 1, 1 '-bis (2, 4, 6- trimethylphenyl) -4,4'-dipyridinium; 1- (3,5-dimethoxyphenyl) -1'-methyl-4,4'-dipyridinium; 1-methyl-1'-phenyl-4,4'-dipyridinium; 1-methyl-1 '- (2-methylphenyl) -4,4'-dipyridinium 1- (4-methoxyphenyl) -1' -methyl-4,4 '-dipyridinium; 1-methyl-1 '- (2,4,6-trimethylphenyl) -4,4'-dipyridinium; 1, 2, 6-trimethyl-1'-phenyl-4,4'-dipyridinium; 1,1'-dimethyl-2,6-diphenyl-4,4'-dipyridinium; 1,1 '-bis (3-phenyl (n-propyl)) -4,4'-dipyridinium; 1,1'-dimethyl-4, '-dipyridinium; 1,1'-dimethyl-2- (3-phenyl (n-propyl)) -4,4'-dipyridinium; 1,1'-dimethyl-4,4 '- (1, 3, 5-triazine-2,4-diyl) dipyridinium; 1,1'-dibenzyl-2, 2 ', 6,6'-tetramethyl-4,4'-dipyridinium; 1,1 '-ethylene-4,4'-dimethyl-2, 2'-dipyridinium; and 1,1 '-dimethyl-2,2' -bis (3-phenyl (n-propyl)) -4,4'-dipyridinium and wherein at least three electroactive species include at least one anode material that is selected of the group consisting of: N, N, N ', N' -tetramethyl-p-phenylenediamine; 2,5, 10-trimethyl-3-phenyl-5,10-dihydrophenazine; 5-ethyl-10-methyl-5,10-dihydrofenazine; 5, 10-dimethyl-5, 10-dihydrobenzo (A) phenazine; 2,7-diphenoxy-5,10-dimethyl-5,10-dihydrophenazine; 2-phenoxy-5, 10-dimethyl-5,10-dihydrophenazine; 2, 7-bis (o-tolyl) -5,10-dimethyl-5,10-dihydrophenazine; 2,3-dimethyl-7-trifluoromethyl-5,10-diethyl-5,10-dihydrophenazine; 5, 10-dimethyl-5,10-dihydrophenazine; 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine; 2,7-diphenyl-5,10-dimethyl-5,10-dihydrophenazine; 2-vinyl-5, 10-dimethyl-5,10-dihydrophenazine; 2-phenyl-5,10-dimethyl-5,10-dihydrophenazine; 5,10-diisopropyl-5,10-dihydrophenazine; 5, 10-dimethyl-5,10-dihydrodibenzo (A, C) phenazine; 1,5, 10-trimethyl-2-phenyl-5,10-dihydrophenazine; 2,3,5,10-tetramethyl-7-trifluoromethyl-5,10-dihydrofenazine and 2,3,5,10-tetramethyl-5,10-dihydrobenzo (B) phenazine.
53. The electrochromic mirror according to claim 38, characterized in that at least three electroactive species include approximately 17 millimolar of 5,10-dimethyl-5,10-dihydrophenazine, approximately 8.5 millimolar of 2-phenyl-5,10-dimethyl. -5,10-dihydrophenazine, about 4.3 millimolar of 2,3-diphenyl-5,10-dimethyl-5,10-dihydrofenazine, about 17 millimolar of 1,1'-dibenzyl-2'-bis (tetrafluoroborate), 6,6 '-tetramethyl-4,4'-dipyridinium and approximately 17 millimolar of bis (hexafluorophosphate) of 1,1'-ethylene-4,4'-dimethyl-2,2'-dipyridinium.
54. The electrochromic mirror according to claim 38, characterized in that at least three electroactive species include approximately 17 millimolar of 5,10-dimethyl-5,10-dihydrophenazine, approximately 8.5 millimolar of 2-phenyl-5,10-dimethyl. -5,10-dihydrophenazine, approximately 4.3 millimolar of 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 19 millimolar of 1,1'-dibenzyl-2,2'-bis (tetrafluoroborate), 6,6'-tetramethyl-4,4'-dipyridinium and approximately 15 millimolar of bis (hexafluorophosphate) of 1,1'-ethylene-4,4'-dimethyl-2,2'-dipyridinium.
55. The electrochromic mirror according to claim 38, characterized in that the preselected color is a member of the group consisting of red, yellow, green, blue, purple and gray.
56. The electrochromic mirror according to claim 55, characterized in that the pre-selected color is gray.
57. The electrochromic mirror according to claim 56, characterized in that at least one of the electroactive materials includes a 5,10-dialkyl-5,10-dihydrophenazine wherein at least one of the 2, 3, 7 and 7 positions 8 contains a member of the group consisting of: phenyl; substituted phenyl; vinyl and phenoxy.
58. The electrochromic mirror according to claim 57, characterized in that at least one of the electroactive materials includes a cathodic electrochromic material that is selected from the group consisting of salts of: 1,1'-diphenyl-4,4 '- dipyridinium, 1,1'-bis (2,6-dimethylphenyl) -4,4'-dipyridinium; 1,1 '-bis (3,5-dimethylphenyl) -4,4'-dipyridinium; 1-phenyl-1 '- (4-dodecylphenyl) -4,4'-dipyridinium; 1,1-bis (2,4,6-trimethylphenyl) -4,4'-dipyridinium; 1- (3,5-dimethoxyphenyl) -1 '-methyl-4,4'-dipyridinium; 1-methyl-1'-phenyl-4,4'-dipyridinium; 1-methyl-1 '- (2-methylphenyl) -4,4'-dipyridinium 1- (4-methoxyphenyl) -1' -methyl-4,4 '-dipyridinium; 1-methyl-1 '- (2,4,6-trimethylphenyl) -4,4'-dipyridinium; 1, 2, 6-trimethyl-1'-phenyl-4,4'-dipyridinium; 1,1'- dimethyl-2,6,6-diphenyl-4,4'-dipyridinium; 1,1'-bis (3-phenyl (n-propyl)) -4,4'-dipyridinium; 1,1'-dimethyl-4,4'-dipyridinium; 1,1'-dimethyl-2- (3-phenyl (n-propyl)) -4,4'-dipyridinium; 1,1'-dimethyl-4,4 '- (1, 3, 5-triazine-2,4-diyl) dipyridinium; 1,1'-dibenzyl-2, 2 ', 6,6' -tetramethyl-4,4'-dipyridinium; 1,1 '-ethylene-4,4'-dimethyl-2, 2'-dipyridinium; and 1,1 '-dimethyl-2, 2'-bis (3-phenyl (n-propyl)) -4,4'-dipyridinium.
59. The electrochromic mirror according to claim 56, characterized in that the mirror maintains a reflectance spectrum that results in color coordinates, A / 2 degrees, so that C * is between zero and approximately 22.
60. The electrochromic mirror according to claim 59, characterized in that the mirror maintains a reflectance spectrum that results in color coordinates, A / 2 degrees, so that a * is between zero and approximately -18.
61. An electrochromic mirror of variable reflectance for automobile vehicles, characterized in that it comprises: separate front and rear elements, each having front and rear surfaces; a layer of transparent conductive material placed on the rear surface of the front element; a reflector placed on one side of the rear element with the proviso that, if the reflector is on the rear surface of the rear element, then the front surface of the rear element contains a layer of transparent conductive material; and a perimeter sealing member joining the front and rear spaced elements together in a separate relationship to define a chamber therebetween; wherein the chamber contains an electrochromic medium, the electrochromic medium comprises at least three electroactive materials, at least two of which are electrochromic, wherein the redox potentials of all of the electroactive materials that are anodic are within approximately 200. mV among themselves, and where the redox potentials of all the electroactive materials that are cathode are within approximately 200 mV each other.
62. The electrochromic mirror according to claim 61, characterized in that the redox potentials of all the electroactive materials that are anodic are within 60 mV each other, and wherein the redox potentials of all the electroactive materials that are cathode are within 60 mV between them.
63. The electrochromic mirror according to claim 62, characterized in that the redox potentials of all the electroactive materials that are anodic are within 40 mV each other, and wherein the redox potentials of All electroactive materials that are cathode are within 40 mV each other.
64. The electrochromic mirror according to claim 61, characterized in that at least three electroactive species include at least one cathodic material that is selected from the group consisting of salts of: 1,1 '-diphenyl-4,4' - dipyridinium, 1,1'-bis (2,6-dimethylphenyl) -4,4'-dipyridinium; 1,1 '-bis (3,5-dimethylphenyl) -4,4'-dipyridinium; 1-phenyl-1 '- (4-dodecylphenyl) -4,4'-dipyridinium; 1,1'-bis (2,4,6-trimethylphenyl) -4,4'-dipyridinium; 1- (3,5-dimethoxyphenyl) -1 '-methyl-4,4'-dipyridinium; 1-methyl-1'-phenyl-4,4'-dipyridinium; 1-methyl-1 '- (2-methylphenyl) -4,4'-dipyridinium 1- (4-methoxyphenyl) -1' -methyl-4, '-dipyridinium; 1-methyl-1 '- (2,4,6-trimethylphenyl) -4,4'-dipyridinium; 1, 2, 6-trimethyl-1'-phenyl-4,4'-dipyridinium; 1,1'-dimethyl-2,6-diphenyl-4,4'-dipyridinium; 1,1 '-bis (3-phenyl (n-propyl)) -4,4'-dipyridinium; 1,1'-dimethyl-4,4'-dipyridinium; 1,1'-dimethyl-2- (3-phenyl (n-propyl)) -4,4'-dipyridinium; 1,1'-dimethyl-4,4 '- (1, 3, 5-triazine-2,4-diyl) dipyridinium; 1,1'-dibenzyl-2, 2 ', 6,6'-tetramethyl-4,4'-dipyridinium; 1,1'-ethylene-4,4'-dimethyl-2, 2'-dipyridinium; and 1,1 '-dimethyl-2, 2'-bis (3-phenyl (n-propyl)) -4,4'-dipyridinium and wherein at least three electroactive species include at least one anodic material that is selected of the group consisting of: N, N, N ', N' -tetramethyl-p-phenylenediamine; 2,5, 10-trimethyl-3-phenyl-5,10-dihydrophenazine; 5-ethyl-10-methyl-5,10-dihydrofenazine; 5, 10-dimethyl-5, 10- dihydrobenzo (A) phenazine; 2,7-diphenoxy-5,10-dimethyl-5,10-dihydrophenazine; 2-phenoxy-5, 10-dimethyl-5,10-dihydrophenazine; 2, 7-bis (o-tolyl) -5,10-dimethyl-5,10-dihydrophenazine; 2,3-dimethyl-7-trifluoromethyl-5,10-diethyl-5,10-dihydrophenazine; 5, 10-dimethyl-5,10-dihydrophenazine; 2, 3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine; 2,7-diphenyl-5,10-dimethyl-5,10-dihydrophenazine; 2-vinyl-5, 10-dimethyl-5,10-dihydrophenazine; 2-phenyl-5,10-dimethyl-5,10-dihydrophenazine; 5,10-diisopropyl-5,10-dihydrophenazine; 5, 10-dimethyl-5,10-dihydrobenzo (A, C) phenazine; 1, 5, 10-trimethyl-2-phenyl-5,10-dihydrophenazine; 2,3,5,10-tetramethyl-7-trifluoromethyl-5,10-dihydrofenazine and 2,3,5,10-tetramethyl-5,10-dihydrobenzo (B) phenazine.
65. The electrochromic mirror according to claim 61, characterized in that at least three electroactive species include approximately 17 millimolar of 5,10-dimethyl-5,10-dihydrophenazine, approximately 8.5 millimolar of 2-phenyl-5,10-dimethyl. -5,10-dihydrophenazine, about 4.3 millimolar of 2,3-diphenyl-5,10-dimethyl-5,10-dihydrofenazine, about 17 millimolar of 1,1'-dibenzyl-2,2'-bis (tetrafluoroborate), 6,6 '-tetramethyl-4,4'-dipyridinium and approximately 17 millimolar of bis (hexafluorophosphate) of 1,1'-ethylene-4,4'-dimethyl-2,2'-dipyridinium.
66. The electrochromic mirror according to claim 61, characterized in that at least three electroactive species include about 17 millimolar of 5,10-dimethyl-5,10-dihydrofenazine, about 8.5 millimolar of 2-phenyl-5,10-dimethyl-5,10-dihydrophenazine, about 4.3 millimolar of 2,3-diphenyl-5 , 10-dimethyl-5,10-dihydrofenazine, approximately 19 millimolar of 1,1'-dibenzyl-2, 2 ', 6,6' -tetramethyl-4,4'-dipyridinium bis (tetrafluoroborate) and approximately 15 millimolar of bis (hexafluorophosphate) of 1,1 '-ethylene-4,4'-dimethyl-2,2'-dipyridinium.
67. The electrochromic mirror according to claim 61, characterized in that the preselected perceived color is a member of the group consisting of red, yellow, green, blue, purple and gray.
68. The electrochromic mirror according to claim 67, characterized in that the pre-selected color is gray.
69. The electrochromic mirror according to claim 68, characterized in that at least one of the electroactive materials includes a 5,10-dialkyl-5,10-dihydrophenazine wherein at least one of the 2, 3, 7 and 7 positions 8 contains a member of the group consisting of: phenyl; substituted phenyl; vinyl and phenoxy.
70. The electrochromic mirror according to claim 68, characterized in that at least one of the electroactive materials includes an electrochromic material cathodic which is selected from the group consisting of salts of: 1,1 '-diphenyl-4,4'-dipyridinium, 1,1'-bis (2,6-dimethylphenyl) -4,4'-dipyridinium; 1,1 '-bis (3,5-dimethylphenyl) -4,4'-dipyridinium; 1-phenyl-1 '- (4-dodecylphenyl) -4,4'-dipyridinium; l, 1-bis (2,4,6-trimethylphenyl) -4,4'-dipyridinium; 1- (3,5-dimethoxyphenyl) -1'-methyl-4,4'-dipyridinium; 1-methyl-1'-phenyl-4,4'-dipyridinium; 1-methyl-1 '- (2-methylphenyl) -4,4'-dipyridinium 1- (4-methoxyphenyl) -1' -methyl-4,4 '-dipyridinium; 1-methyl-1 '- (2,4,6-trimethylphenyl) -4,4'-dipyridinium; 1, 2, 6-trimethyl-1'-phenyl-4,4'-dipyridinium; 1,1'-dimethyl-2,6-diphenyl-4,4'-dipyridinium; 1, 1 '-bis (3-phenyl (n-propyl)) -4,4"-dipyridinium; 1,1'-dimethyl-4,4'-dipyridinium; 1,1'-dimethyl-2- (3 - phenyl (n-propyl)) -4,4'-dipyridinium; 1,1'-dimethyl-4,4 '- (1,3,5-triazine-2,4-diyl) dipyridinium; 1,1'-dibenzyl; -2.2 ', 6,6' -tetramethyl-4,4'-dipyridinium; 1,1'-ethylene-4,4'-dimethyl-2,2'-dipyridinium; and 1,1 '-dimethyl-2 , 2'-bis (3-phenyl (n-propyl)) -4,4'-dipyridinium
71. The electrochromic mirror according to claim 68, characterized in that the mirror maintains a reflectance spectrum that results in color coordinates. , A / 2 degrees, so that C * is between zero and approximately 22.
72. The electrochromic mirror according to claim 71, characterized in that the mirror maintains a reflectance spectrum that results in color coordinates, A / 2 degrees, so that a * is between zero and approximately -18.
73. The electrochromic device according to one of claims 1 and 25, characterized in that the electrochromic means is gray and in which the transparent conductor of the rear surface or of the front element lacks color.
74. The electrochromic device according to one of claims 38 and 61, characterized in that the electrochromic medium is gray and the transparent conductor on the rear surface of the front element is colorless.
75. The electrochromic device according to claim 74, characterized in that the reflector is white.
76. A compound characterized in that it has the formula: wherein: R-_, R4, R6 and Rs are the same or different and are selected from the group consisting of: hydrogen and alkyl from i to i2; R2, R3, R7 and R8 are the same or different and are selected from the group consisting of: hydrogen, alkenyl, Cx to C12 alkyl, aryl, substituted aryl, alkoxy, phenoxy and halogenated alkanes of C2 to C12, wherein minus one of R2, R3, R7 or R8 is hydrogen; R5 and Rio are the same or different and are selected from the group consisting of: linear and branched alkyl from Cx to C3; and if R5 and Rio are both linear alkyl, then at least one of R2, R3, R7 and R8 are the same or different and are selected from the group consisting of: alkenyl, Cx to C12 alkyl, aryl, substituted aryl, alkoxy , phenoxy and halogenated alkanes of C to C 2, with at least one of R 2, R 3, R 7 or R 8 which is hydrogen; but if R5 and R10 are methyl, and Rx, R3, R6, R8 and R9 are hydrogen, then R2 and R7 are not both methyl, phenyl or methoxy; if R? ~ R2 is benzo and R4 is hydrogen or if R3-R4 is benzo and Ri is hydrogen, or if R2-R3 is benzo, then R5 and R10 are the same or different and are selected from the group consisting of: linear alkyl and branched from Cx to C3, and R6, R7, R8 and R9 are same or different and are selected from the group consisting of: Cx to C12 alkyl and hydrogen; and if R6-R7 is benzo and R9 is hydrogen, or if R8-R9 is benzo and R6 is hydrogen or if R7-R8 is benzo, then R5 and R10 are the same or different and are selected from the group consisting of: linear alkyl and branched from Cx to C3, and R6, R7, R8 and R9 are the same or different and are selected from the group consisting of: alkyl and hydrogen.
77. The compound according to claim 1, characterized in that Rx, R4, R6 and R9 are the same or different and are selected from the group consisting of: hydrogen and methyl; R2, R3, R7 and R8 are the same or different and are selected from the group consisting of: methyl, phenyl, vinyl, alkoxy, phenoxy, tolyl, trifluoromethyl and hydrogen with at least one of R2, R3, R7 or R8 constituted by hydrogen; 5 and Rio are the same or different and are selected from the group consisting of methyl, ethyl, and isopropyl; if either of R5 or R10 is methyl or ethyl, then R2 is selected from the group consisting of: methyl, phenyl, vinyl, phenoxy, tolyl and trifluoromethyl.
78. The compound according to claim 77, characterized in that at least one of R2, R3, R7 and R8 is O-tolyl.
79. The compound according to claim 76, characterized in that if R2 is aryl, then Rx is Cx to Ci2 alkyl, or R3 is selected from the group consisting of: CL to C12 alkyl, aryl, substituted aryl, alkenyl, alkoxy, phenoxy and halogenated alkanes of Cx to C12; if R3 is aryl, then R4 is a Cx to C12 alkyl or R2 is selected from the group consisting of: alkenyl, Cx to C12 alkyl, aryl, substituted aryl, alkoxy, phenoxy and halogenated alkanes of C to C12; if R7 is aryl, then R6 is a Cx to C12 alkyl; or R8 is selected from the group consisting of: C alkyl? to C12, aryl, substituted aryl, alkenyl, alkoxy, phenoxy and halogenated alkanes of Cx to C12; if R8 is aryl, then R9 is a Cx to C2 alkyl, or R7 is selected from the group consisting of: C to C12 alkyl, aryl, substituted aryl, alkenyl, alkoxy, phenoxy and halogenated alkanes of Cx to C12 .
80. The compound according to claim 76, characterized in that it has the formula selected from the group consisting of: 2-vinyl-5, 10-dimethyl-5, 10-dihydrophenazine; 2,7- (o-tolyl) -5,10-dimethyl-5,10-dihydrophenazine; 2, 3-dimethyl-7-trifluoromethyl-5,10-diethyl-5,10-dihydrophenazine; 2, 3, 5, 10-tetramethyl-7-trifluoromethyl-5,10-dihydrophenazine; 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine; 2, 5, 10-trimethyl-3-phenyl-5,10-dihydrophenazine; 5,10-diisopropyl-5,10-dihydrophenazine; 2,3,5,10-tetramethyl-5,10-dihydrobenzo (B) -phenazine; 5, 10-dimethyl-5,10-dihydrobenzo (A) phenazine; 2-phenoxy-5, 10-dimethyl-5,10-dihydrophenazine; 2, 7-diphenoxy-5, 10-dimethyl- 5, 10 -dihydrofenazine; 1, 5, 10-trimethyl-2-phenyl-5,10-dihydro-phenazine; and 2-phenyl-5,10-dimethyl-5,10-dihydrophenazine.
81. A salt of the compound having the formula: characterized in that if Rx is phenyl substituted with methoxy, or a phenyl substituted with trimethyl, R ±, is alkyl having 1 to 9 carbons, R2, R2 ,, Rs and R6, are hydrogen; if Ri is phenyl and Rx is methyl, then R2 and R6 are hydrogen and R2 and R6 are aralkyl or alkyl having 1 to 9 carbons; if R-L and Ri, are m-xylyl and R2, R2, R6 and R6 are hydrogen; if Ri is phenyl and Rlt is substituted aryl having 18 carbons, and R2, R2, R6 and R6, are hydrogen; or if R x and R x are methyl, R 2 is aralkyl having 8 or 9 carbons or alkyl having 6 carbons, and R 2, R 6 and R 6 are the same or different and are selected from the group that is select hydrogen and alkyl and aralkyl having from 1 to 9 carbons.
82. The salts according to claim 81, characterized in that the anion is selected from the group consisting of: tetrafluoroborate, hexafluorophosphate, perchlorate and a halide.
83. A method in a container, characterized in that it comprises the steps of: (a) mixing a heterocyclic azine compound; a reducing reagent; one base; an alkylating reagent; a member of the group consisting of: a phase transfer catalyst, water or both a phase transfer heat such as water, and a solvent in a vessel; (b) stirring the mixture under an inert atmosphere; and (c) separating a compound from the mixture, wherein the heterocyclic azine compound is reduced and alkylated.
84. The method according to claim 83, characterized in that the alkylating reagent is selected from the group consisting of alkyl halides and alkyl sulfonates.
85. The method according to claim 83, characterized in that the temperature at which the mixture is heated is the reflux temperature of the mixture.
86. The method according to claim 83, characterized in that the solvent is a polar aprotic solvent.
87. A two-phase method, in a container, characterized in that it comprises the steps of: (a) mixing a heterocyclic azine compound; a reducing reagent; one base; an alkylating reagent; a member of the group consisting of: a phase transfer catalyst, water or both a phase transfer catalyst such as water, and a non-polar solvent, in a container; (b) stirring the mixture of two bases under an inert atmosphere; and (c) separating a compound from the two phase mixture, wherein the heterocyclic azine compound is reduced and alkylated.
88. The method according to claim 83, characterized in that the method is used to produce the compounds of the formula: wherein: Rx, R4, R6 and R9 are the same or different and are selected from the group consisting of: hydrogen and alkyl of (C2) R2, R3, R7 and R8 are the same or different and are selected from the group consisting of: a group consisting of: hydrogen, alkenyl, Cx to C12 alkyl, aryl, substituted aryl, alkoxy, phenoxy and halogenated alkanes of Cx to Cx2, wherein at least one of R2, R3, R7 or R8 is hydrogen; and R? 0 are the same or different and are selected from the group consisting of: linear and branched alkyl from Cx to C3, and if R5 and Rxo are both linear alkyl, then at least one of R2, R3, R7 and R8 are same or different and are selected from the group consisting of: alkenyl, Cx to C12 alkyl, aryl, substituted aryl, alkoxy, phenoxy and halogenated alkanes of Cx to C12, with at least one of R2, R3, R7 or R8 constituted by hydrogen, if R? ~ R2 is benzo and R4 is hydrogen or if R3-R4 is benzo and Ri is hydrogen, or if R2-R3 is benzo, then R5 and R? 0 are the same or different s and are selected from the group consisting of: linear and branched alkyl from Cx to C3, and R6, R7, R8 and R9 are the same or different and are selected from the group consisting of: Cx to C2 alkyl and hydrogen; and if R6-R7 is benzo and R9 is hydrogen, or if R8-R9 is benzo and R6 is hydrogen or if R7-R8 is benzo, then R5 and Rx0 they are the same or different and are selected from the group consisting of: linear and branched alkyl from Cx to C3, and R6, R7, R8 and R9 are the same or different and are selected from the group consisting of: alkyl and hydrogen.
89. The method according to claim 83, characterized in that the method is used to produce compounds that are selected from the group consisting of: 2-vinyl-5, 10-dimethyl-5, 10-dihydrophenazine; 2,7-bis (o-tolyl) -5,10-dimethyl-5,10-dihydrophenazine; 2,3-dimethyl-7-trifluoromethyl-5,10-diethyl-5,10-dihydrophenazine; 2,3,5,10-tetramethyl-7-trifluoromethyl-5, 10.dihydrophenazine; 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine; 2,5, 10 -trimethyl-3-phenyl-5,10-dihydro-phenazine; 5,10-diisopropyl-5,10-dihydrophenazine; 2,3,5,10-tetramethyl-5,10-dihydrobenzo (B) phenazine; 5, 10-dimethyl-5,10-dihydrobenzo (A) phenazine; 2-phenoxy-5, 10-dimethyl-5,10-dihydro-phenazine; 2,7-diphenoxy-5,10-dimethyl-5,10-dihydrophenazine; 1,5, 10-trimethyl-2-phenyl-5,10-dihydrophenazine; 2-phenyl-5,10-dimethyl-5,10-dihydrophenazine; and 2,7-diphenyl-5,10-dimethyl-5,10-dihydrophenazine.
90. The method according to claim 83, characterized in that the compound having bound heteroatoms is selected from the group consisting of phenazines, triphenodia thiazines, trif-enodioxazes, quinoxalinophenazines, dyes based on phenoxazine and dyes based on phenothiazine.
91. The method according to claim 83, characterized in that the stirring step includes the application of heat to the mixture.
92. The method according to claim 83, characterized in that the separation step comprises the steps of adding water and filtering and separating the alkylated compound.
93. The method according to claim 83, characterized in that the water is less than about 20 volume percent of the mixture and wherein the phase transfer catalyst is methyltributylammonium chloride and is present at about 0.1 mole percent of mix.
94. The method according to claim 83, characterized in that the phase transfer is an accessible quaternary ammonium salt.
95. The method according to claim 83, characterized in that the base is a metal carbonate salt.
96. The method according to claim 83, characterized in that the reducing agent is selected from the group consisting of: sodium hydrosulfite and hydrophosphorous acid.
97. The method according to claim 83, characterized in that the azine compound The heterocyclic compound is selected from the group comprising phenazines, triphenynediazines, triphenoxazines, quinoxalinophenazines, phenazine-based dyes, phenoxazine-based dyes and phenothiazine-based dyes.
98. The salts according to claim 81, characterized in that Rx and Rx ,, are m-xylyl linked in the 2 or 5 position, and R2, R2, R6 and R6 are hydrogen.
99. The salts according to claim 81, characterized in that Rx is phenyl, Rx is substituted phenyl having 18 carbons and R2, R2, R6 and R6 are hydrogen.
100. The salts according to claim 81, characterized in that Rx and Rx are methyl, R2 is selected from the group of phenylpropyl, phenylethyl and n-hexyl, and R2 ,, R6 and R6 are the same or different and are selected from the group consisting of hydrogen group, alkyl having 1 to 6 carbons, phenylpropyl and phenylethyl.
101. The salts according to claim 81, characterized in that the salts are selected from the group of 1,1'-bis (2,6-dimethylphenyl) -4,4'-dipyridinium; 1; 1'-bis (3,5-dimethylphenyl) -4,4'-dipyridinium; 1-phenyl-1 '- (4-dodecylphenyl) -4,4'-dipyridinium; 1- (3,5-dimethoxyphenyl) -1'-methyl-4,4'-dipyridinium; 1- (4-methoxyphenyl) -1 '-methyl-4,4'-dipyridinium; 1-methyl-1 '- (2,4,6-trimethylphenyl) -4,4'-dipyridinium; 1, 2, 6-trimethyl-1'-phenyl-4,4'-dipyridinium; 1,1'- dimethyl-2- (3-phenyl (n-propyl)) -4, -dipyridinium; 1,1'-dimethyl-2- (2-phenylethyl) -4,4'-dipyridinium; 1,1'-dimethyl-2, 2'-bis (3-phenyl (n-propyl)) -4,4'-dipyridinium; 1,1'-dimethyl-2, 2'-bis (2-phenylethyl) -4,4'-dipyridinium; 2,2 ', 6-trimethyl-6' - (3-phenyl (n-propyl)) -4,4'-dipyridinium; 1, 1 ', 2, 2', 6-pentamethyl-6 ', 2-phenylethyl-4,4'-dipyridinium; 1,1 ', 2,2'-tetramethyl-6,6' -bis (2-phenylethyl) -4,4'-dipyridinium; 1,1 ', 2-trimethyl-2', 6,6 '-tris (2-phenylethyl) -4,4'-dipyridinium; and 1, 1 ', 2,', 6-pentamethyl-6'-hexyl-4,4'-dipyridinium.
102. An electrochromic device, characterized in that it comprises: separate front and rear elements, each having front and rear surfaces; a layer of transparent conductive material placed on the rear surface of the front element and the front surface of the rear element, and a perimeter sealing member joining together the separate front and rear elements in a separate relation to define a chamber therebetween; and wherein the chamber contains an electrochromic medium, the electrochromic means comprises at least three electroactive materials, at least two of which are electrochromic, whose concentrations are chosen to produce a preselected perceived color, wherein the device does not show graduation.
103. An electrochromic device, characterized in that it comprises: separate front and rear elements, each having front and rear surfaces; a layer of transparent conductive material placed on the rear surface of the front element and the front surface of the rear element, and a perimeter sealing member joining together the separate front and rear elements in a separate relation to define a chamber therebetween; and wherein the chamber contains an electrochromic medium, the electrochromic means comprises at least three electroactive materials, at least two of which are electrochromic, wherein the device maintains a transmittance spectrum that results in color coordinates, D65 / 2 degrees, so that C * is between zero and approximately 22.
104. The electrochromic device according to claim 103, characterized in that the device maintains a transmittance spectrum that results in color coordinates, D65 / 2 degrees so that a * is between zero and approximately -18.
105. An electrochromic device, characterized in that it comprises: separate front and rear elements, each has front and rear surfaces; a layer of transparent conductive material placed on the rear surface of the front element and on the front surface of the rear element, and a perimeter sealing member joining together the separate front and rear elements in a separate relation to define a chamber therebetween; and wherein the chamber contains an electrochromic medium, the electrochromic means comprises at least three electroactive materials, at least two of which are anodic electrochromic compounds and at least one is generally a colorless cathode electroactive compound in two oxidation states.
106. The electrochromic device according to claim 105, characterized in that the anodic electrochromic compounds are confined on the surface.
107. The electrochromic device according to claim 105, characterized in that the camera further includes a member of the group consisting of a substance that absorbs light, a stabilizer before light, a thermal stabilizer, an antioxidant, a thickener or a gel of free lift.
108. An electrochromic device, characterized in that it comprises: separate front and rear elements, each has front and rear surfaces; a layer of transparent conductive material placed on the rear surface of the front element and the front surface of the rear element, and a perimeter sealing member joining together the separate front and rear elements in a separate relation to define a chamber therebetween; and wherein the chamber contains an electrochromic medium, the electrochromic medium comprises at least three electroactive materials, at least two of which are cathode compounds and at least one is generally a colorless anodic electroactive compound in two oxidation states.
109. The electrochromic device according to claim 108, characterized in that the cathode electrochromic compounds are confined to the surface.
110. The electrochromic device according to claim 108, characterized in that the chamber further includes a member of the group consisting of a substance that absorbs light, a stabilizer before light, a thermal stabilizer, an antioxidant, a thickener or a gel of free lift.
111. An electrochromic device, characterized in that it comprises: separate front and rear elements, each has front and rear surfaces; a layer of transparent conductive material placed on the rear surface of the front element and the front surface of the rear element, and a perimeter sealing member joining together the separate front and rear elements in a separate relation to define a chamber therebetween; and wherein the chamber contains an achromatic electrochromic medium, the electrochromic means comprises at least three electroactive materials, at least two of which are electrochromic.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08832596 | 1997-04-02 |
Publications (1)
Publication Number | Publication Date |
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MXPA99008945A true MXPA99008945A (en) | 2000-06-01 |
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