CA2246478A1 - Electrochromic system - Google Patents
Electrochromic system Download PDFInfo
- Publication number
- CA2246478A1 CA2246478A1 CA002246478A CA2246478A CA2246478A1 CA 2246478 A1 CA2246478 A1 CA 2246478A1 CA 002246478 A CA002246478 A CA 002246478A CA 2246478 A CA2246478 A CA 2246478A CA 2246478 A1 CA2246478 A1 CA 2246478A1
- Authority
- CA
- Canada
- Prior art keywords
- represent
- another
- independently
- bridge
- formulae
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000126 substance Substances 0.000 claims abstract description 38
- 102100038191 Double-stranded RNA-specific editase 1 Human genes 0.000 claims abstract description 12
- 101000742223 Homo sapiens Double-stranded RNA-specific editase 1 Proteins 0.000 claims abstract description 12
- 101000686491 Platymeris rhadamanthus Venom redulysin 1 Proteins 0.000 claims abstract description 12
- 239000012476 oxidizable substance Substances 0.000 claims abstract description 9
- 238000002835 absorbance Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 238000001228 spectrum Methods 0.000 claims abstract description 3
- 241000682622 Andracantha sigma Species 0.000 claims abstract 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 45
- 239000001257 hydrogen Substances 0.000 claims description 43
- -1 cyclic organic compound Chemical class 0.000 claims description 37
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 30
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 15
- 239000012530 fluid Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- BUYUFJZVMVFQLQ-UHFFFAOYSA-N 4-[2-(5,5,8,8-tetramethyl-6,7-dihydroquinoxalin-2-yl)ethynyl]benzoic acid Chemical compound CC1(C=2N=CC(=NC=2C(CC1)(C)C)C#CC1=CC=C(C(=O)O)C=C1)C BUYUFJZVMVFQLQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 6
- 102100024692 Double-stranded RNA-specific editase B2 Human genes 0.000 claims description 5
- 101000686486 Homo sapiens Double-stranded RNA-specific editase B2 Proteins 0.000 claims description 5
- 101000686495 Platymeris rhadamanthus Venom redulysin 2 Proteins 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- WPPDXAHGCGPUPK-UHFFFAOYSA-N red 2 Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C=3C4=CC=C5C6=CC=C7C8=C(C=9C=CC=CC=9)C9=CC=CC=C9C(C=9C=CC=CC=9)=C8C8=CC=C(C6=C87)C(C=35)=CC=2)C4=C1C1=CC=CC=C1 WPPDXAHGCGPUPK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 150000003519 bicyclobutyls Chemical class 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 150000001942 cyclopropanes Chemical class 0.000 claims description 4
- UCFFGYASXIPWPD-UHFFFAOYSA-N methyl hypochlorite Chemical compound COCl UCFFGYASXIPWPD-UHFFFAOYSA-N 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 3
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- YTZPUTADNGREHA-UHFFFAOYSA-N 2h-benzo[e]benzotriazole Chemical class C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 2
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 16
- 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 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical class C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 claims 1
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 claims 1
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003776 cleavage reaction Methods 0.000 abstract 1
- 230000007017 scission Effects 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 description 23
- 150000003254 radicals Chemical class 0.000 description 21
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 230000009467 reduction Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 239000012039 electrophile Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000012038 nucleophile Substances 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 2
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- FMRHJJZUHUTGKE-UHFFFAOYSA-N Ethylhexyl salicylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1O FMRHJJZUHUTGKE-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- JGTNAGYHADQMCM-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-M 0.000 description 1
- YGTAZGSLCXNBQL-UHFFFAOYSA-N 1,2,4-thiadiazole Chemical compound C=1N=CSN=1 YGTAZGSLCXNBQL-UHFFFAOYSA-N 0.000 description 1
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical compound C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 description 1
- DTSPMBOMCCTXSG-UHFFFAOYSA-N 1,3-dimethylidenecyclobutane Chemical class C=C1CC(=C)C1 DTSPMBOMCCTXSG-UHFFFAOYSA-N 0.000 description 1
- QXBUYALKJGBACG-UHFFFAOYSA-N 10-methylphenothiazine Chemical compound C1=CC=C2N(C)C3=CC=CC=C3SC2=C1 QXBUYALKJGBACG-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 description 1
- OJWYYSVOSNWCCE-UHFFFAOYSA-N 2-methoxyethyl hypofluorite Chemical compound COCCOF OJWYYSVOSNWCCE-UHFFFAOYSA-N 0.000 description 1
- FPPLREPCQJZDAQ-UHFFFAOYSA-N 2-methylpentanedinitrile Chemical compound N#CC(C)CCC#N FPPLREPCQJZDAQ-UHFFFAOYSA-N 0.000 description 1
- KQZBSZUGKSCFBL-UHFFFAOYSA-N 2-phenyldiazenylaniline Chemical class NC1=CC=CC=C1N=NC1=CC=CC=C1 KQZBSZUGKSCFBL-UHFFFAOYSA-N 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- BCGCCTGNWPKXJL-UHFFFAOYSA-N 3-(2-cyanoethoxy)propanenitrile Chemical compound N#CCCOCCC#N BCGCCTGNWPKXJL-UHFFFAOYSA-N 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 235000003625 Acrocomia mexicana Nutrition 0.000 description 1
- 244000202285 Acrocomia mexicana Species 0.000 description 1
- 102100038916 Caspase-5 Human genes 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 241001663154 Electron Species 0.000 description 1
- 101100112336 Homo sapiens CASP5 gene Proteins 0.000 description 1
- 101100273286 Mus musculus Casp4 gene Proteins 0.000 description 1
- YBGZDTIWKVFICR-JLHYYAGUSA-N Octyl 4-methoxycinnamic acid Chemical compound CCCCC(CC)COC(=O)\C=C\C1=CC=C(OC)C=C1 YBGZDTIWKVFICR-JLHYYAGUSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- IAJNXBNRYMEYAZ-UHFFFAOYSA-N ethyl 2-cyano-3,3-diphenylprop-2-enoate Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC)C1=CC=CC=C1 IAJNXBNRYMEYAZ-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000004761 hexafluorosilicates Chemical class 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- WOFDVDFSGLBFAC-UHFFFAOYSA-N lactonitrile Chemical compound CC(O)C#N WOFDVDFSGLBFAC-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical class C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 150000004060 quinone imines Chemical class 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Plural Heterocyclic Compounds (AREA)
Abstract
The electrochromic system proposed contains at least one oxidizable substance RED1 and at least one reducible substance OX2 each of which changes from a colourless or only slightly coloured form into a coloured form by virtue of an increase in the absorbance in the visible region of the spectrum. The system is characterized in that the conversion of the oxidizable form into the reducible form and vice versa occurs by cleavage or formation of a .sigma.bond.
Description
Le A 31 464-Foreign Countries / WlC/ngb/S-P
I
FIL'L~
El~ svstem IE~i IP~ .r!'-L~lTiUN
The present invention relates to an ch,~,L-uvll.u...;c system, an clc~ ,l..ulll;c fluid S comprising this ch,~ uvLu~dv system, and an el~-l.uvll.u;c device.
El~ uvh-ull,;c devices which contain an CICvllUvlllUllliC system are already known .
Such devices customarily contain, as the eLvL-u~ system, redox couples which are dissolved in an inert solvent. Additionally, conducting salts, light stabilizers arid substances which affect the viscosity may be included.
Used as a redox couple is one reducible and one oxidizable substance each. Both are colorless or oniy;weakly colored. Under the influence of an electric voltage, one of the substances is reduced and the other is oxidized, at least one becoming colored in the process. After the voltage is switched off, the two original redox substances are formed once more, ~c~mp-r:cd by bleaching or fading of the color.
RED, + ~X2 ~ OX~ + RED2 (colorless) (colored) (low-energy couple) (high energy couple) US 4,9û2,1û8 discloses that those redox couples are suitable in which the reducible substance at least exhibits two chemically reversible reduction waves in ' 20 the cyclic v~ -, and the oxidizable substance vu--~,' ' "'y exhibits at least two chemically reversible oxidation waves.
Electrochromic devices can be used in many different ways. For example, they may take the form of a car rearview mirror which during a journey at night can be darkened by a voltage beirig applied and thus prevents dazzling by the headlights of other vehicles (compare e.g. US 3,280,701, US 4,902,108, EP-A-0,435,689).
Such devices may further also be employed in window panes or car canopies where, after a voltage has been applied~ they black out the sunligbt Finally, such devices may also bc used to build up a matrix display for graphic representationof information such as letters, numbers and symbols Le A 31 464-Forei~n Countries
I
FIL'L~
El~ svstem IE~i IP~ .r!'-L~lTiUN
The present invention relates to an ch,~,L-uvll.u...;c system, an clc~ ,l..ulll;c fluid S comprising this ch,~ uvLu~dv system, and an el~-l.uvll.u;c device.
El~ uvh-ull,;c devices which contain an CICvllUvlllUllliC system are already known .
Such devices customarily contain, as the eLvL-u~ system, redox couples which are dissolved in an inert solvent. Additionally, conducting salts, light stabilizers arid substances which affect the viscosity may be included.
Used as a redox couple is one reducible and one oxidizable substance each. Both are colorless or oniy;weakly colored. Under the influence of an electric voltage, one of the substances is reduced and the other is oxidized, at least one becoming colored in the process. After the voltage is switched off, the two original redox substances are formed once more, ~c~mp-r:cd by bleaching or fading of the color.
RED, + ~X2 ~ OX~ + RED2 (colorless) (colored) (low-energy couple) (high energy couple) US 4,9û2,1û8 discloses that those redox couples are suitable in which the reducible substance at least exhibits two chemically reversible reduction waves in ' 20 the cyclic v~ -, and the oxidizable substance vu--~,' ' "'y exhibits at least two chemically reversible oxidation waves.
Electrochromic devices can be used in many different ways. For example, they may take the form of a car rearview mirror which during a journey at night can be darkened by a voltage beirig applied and thus prevents dazzling by the headlights of other vehicles (compare e.g. US 3,280,701, US 4,902,108, EP-A-0,435,689).
Such devices may further also be employed in window panes or car canopies where, after a voltage has been applied~ they black out the sunligbt Finally, such devices may also bc used to build up a matrix display for graphic representationof information such as letters, numbers and symbols Le A 31 464-Forei~n Countries
- 2 --Electrochromic devices normally comprise a pair of glass or plastic panes, one of which being mirrored in the case of a car mirror One side of these panes is coated with a transparent, electroconductive layer, e.g indium tin oxide (ITO).
These panes are tllen used to construct a cell by being bonded, preferably 5 cemented, to an annular or rectangular gasket so that their ele~llrJco..du~,Liv~ly coated sides face one another. The gasket establishes a uniform spacing between the panes, for example from 0.1 to 0.5 mm. This cell is then, via a port, filledwith an electrochromic solutioll and is tightly sealed. Via the ITO layer contact can be made separately with the two panes.
I() The prior art cl~ ,.,h.e,----c systems comprise redox couples which, after reduc-tion and oxidation, forrn colored free radicals, cationic free radicals or anionic free radicals, which are chemically reactive. As disclosed, for example, by Topics inCurrent Chemistry, ~ol. 92, pp. 1-44 (1980), such (ionic) free radicals may be sensitive with respect to electrophiles or nucleophiles or even free radicals. To 15 achieve a high stability of an electrochromic device containing such an electro-chromic system which is to survive several thousands of operating cycles it is the-refore necessary to ensure that the solvent used is absolutely free from electrophi-les, e.g. protons, nucleophiles and oxygen. It is also necessary to ensure that such reactive species are not formed by electrochemical processes on the electrodes du-20 ring operation of the electrochromic device.
There was therefore a need for an r;le~ wllic system which comprises at leastone ele~ u~,lu~JI..;c substance which after reduction or oxidation is not converted(. . into an (ionic) free radical species but has a closed electron shell in the reduced or oxidized form.
25 The present invention therefore relates to an electrochromic system comprising at least one oxidizable substance REDI which, by releasing electrons at an anode, is converted from a weakly colored or colorless form into a colored form OXI, and at least one reducible substance OX2 which, by accepting electrons at a cathode, is converted from a weakly colored or colorless form into a colored form RED~, the 30 absorbance in the visible region of the spectrum increasing in each of these cases, and the weakly colored or colorless form being recovered in each case after charge equalization, wherein the reciprocal conversion of oxidized and reduciblc form takes place by a c bond being broken or formed, respectivelyl for at least one of the comprised substances REDI or OX2 Le A 31 464-Foreign Countries Preferably, the cl~ ~ c system according to the invention comprises at least one couple of reducible and oxidizable substances RED,/OX2.
The reduction and oxidation processes in the eleu~,( ' u--uc system according tothe invention generally take place by electrons being accepted or released at a cat-S hode or anode, ~ ,ly, a potenhal difference of from 0.3 to 3 V preferablyobtaining between the electrodes. After the electric potential is switched off, charge equalization generally takes place ~p~ ly between the substances RED2 and OXI, r . ~'1 by bleaching or fading of the color. Such a charge equalization also takes place even while the current is flowing in the interior of 10 . the electrolyte volume.
The cl~ -, ~,.nic system according to the invention preferably comprises, as thereducible substance ~2, a cyclic organic compound which, after accepting I or 2 electrons, is converted~ one of the a bonds of the ring being broken, into an open-ring compound and which, by releasing I or 2 electrons, is converted once more 15 into the cyclic starting compound, in each case precisely two electrons being trans-ferred overall, however.
Said nng opening may take place, for example, by two electrons being accepted directly, resulting in breaking of the bond. Alternatively it is possible for one elec-tron to be accepted initially, whereupon ring opening takes place which may then20 be followed by further reactions such as a further electron and/or a proton being accepted and/or an anionic leaving group being eliminated, precisely 2 electrons(~ , being accepted overall, however. Said ring opening results in an altered 7~ electro system which has a corresponding higher-wavelength and/or higher-absorbance light absorption. Ring closure may correspondingly take place by sllllul~d--~,us25 release of two electrons or ::uccc~ ly by release of first one electron and possi-bly a further electron, and/or the proton which may have been bound is eliminated again and/or the eliminated anionic leaving group is bound once more, precisely 2 electrons being released overall, however T he reducible substance OX2 which is comprised in the electrochromic system 30 according to the invention and comprises, as the reducible subslance OX2 whicll is converted reversibly, a ring a bond being broll;en, into the corresponding open-ring substance RED2, is, in particular, a compound selected from the group consistingof the tetrazolium salts, benzo- or napl~thotria701ium salts, cyclopropanes and ~ CA 02246478 1998-08-12 Le A 31 464-Forei~n Countries [I.l.O]bicyclobutanes. As a result of electrons being accepted and bonds breaking~
the ~,u~ hlg colored compounds from the group consisting of the formazans, amino-azo-benzenes, amino-azo-l, ' ' lc.,~, 1,3-dimethylenepropanes and 1,3-dimethylenecyclobutanes are then formed therefrom.
5 The tetrazolium salts, .- lj ' ' of riSf~olium salts, cyclopropanes and [I.l.O]bicyclobu-tanes are preferably those compounds of the formulae (I) to (IV) + ,R4 R~ R3 N=N
+ N--N (l) ~I~N-Rs N ~ N R6~W
R'9 R16 R8 R" ~( ~<~ (111).R~--R (lv) R7 R12 R~5 Rf in which R1 to Rs, inrl~l....r.'..~lly of one another, represent C6- to C1O-aryl or an aromatic or quasi-aromatic five- or six-membered heterocyclic ring, each of which is optionally bl n7sfnf119f~ f.
R7, R9, Rl3 and Rl4, independently of one another, represent a radical of the formulae (V) to (VII) R2n R21 R20 R21 + N R23 ~/ ~, (V), ~ E E R
Le A 31 464-Forei~n Countries R8, RlS and Rl6, h~ ly of one another, represent C~,- to C1O-aryl, C7-CII-aroyl or a radical of the formulae (V) to (Vll), Rl~ to Rl2, Rl7 and Rl8, h,~ of one another, represent hydrogen, Cl- to C4-alkyl, halogen or cyano, S El and E2, ind~r~nd~ntly of one another, represent O, S or N-RI9, Rl9 and R22, ind~rPnd--ntly of one another, represent Cl- to Cl8-alkyl, C2- to C8-alkenyl, C4- to C7-cycloalkyl, C7- to Cl5-aralkyl or C6- tQ Cl0-aryl, .: R6, R20, R21, R23 and R24, h~ 7 of one another, represent hydrogen, Cl-to C4-alkyl, Cl- to C4-alkoxy, halogen, cyano, nitro or Cl- to C4-alkoxycar-bonyl, or R20 and R21, or R23 and R24, jointly forrn a -CH=CH-CH=CH- bndge, and X~ represents a colorless anion which is redox-inert under the conditions Those compounds of formulae (I) to (IV) are preferred in which Rl to R5, independently of one another, represent a radical of the formulae R58 R 9 R5' ~R57 (XlX), ~ R62 (XXj in wl-ich R'7 to R62, independently of one anothcr, represent hydrooen, Cl- to C6-al-kyl, Cl- to C(,-alkoxy, hydroxy, halo~en, cyano, nitro, di-(CI- to 2Q C4-alkyl)a~ o, tri-(CI- to C4-alkyl)aml11oniul-1, C~- to C6-alkanoy-lamino, benzoylamhlo, Cl- to C~,-alkyl-sulfonylamino, benzenesul~o-nylamino, Cl- to C4-alkoxycarbonyl or COOH, or Le A 31 464-Forei~n Countries radicals juxtaposed in pairs jointly form an -O-(CH2)2 3-, -O-(CH2)1 2-O-, -NR63-(CH2)2 3- or -NR53-(CH2)1 2-o- bridge, or R58 and R59 and/or R61 and R62 form a -CH=CH-CH=CH- bridge which may be substituted by methyl, methoxy or chlorine, S R63 represents hydrogen or C1- to C4-alkyl, E12 represents O, S or NR6q, R64 represents hydrogen, C1- to Cl8-alkyl, C2- to C12-alkenyl, C4- to C7-cy cloalkyl, C7- to C15-arallyl or C6- to C10-aryl, R7, R9, R13 and Rl4 represent a radical of formula (V) and are pairwise identical, R8, Rl5 and Rl6 represent phenyl or a radical of formula (V), and R~5 and Rl6 are identical, R6, Rl~ and R12 represent hydrogen, Rl 1 represents hydrogen, methyl, cyano or chlorine, Rl7 and Rl8 represent hydrogen or methyl and are identical, . 15 E1 represents O or NR19, R19 represents C1- to Cl2-alkyl, C2- to C4-alkenyl, cyclohexyl, benzyl or phenyl, R20 and R21 represent hydrogen or jointly form a -CH=CII-CH=CH- bridge, and X~ represents a colorless anion which is redox-inert under the conditions.
The electrochromic system according to the invention, whicll prcferably comprises, as oxidizable substances REDI, those organic compounds which are able to release Le A 31 464-Foreign Countries 2 electrons reversibly in two stages, a higher...~ ,th and/or stronger light absorption being achieved, in particular, after one electron has been released.
In a cyclic voltamn ogram, recorded in an inert solvent, these substances RFDI
exhibit at least 2, as a rule precisely 2, clc~ u~,l.~,.l-ically and chemically reversible S oxidation states which are each caused by an electron being released. Such sub-stances are disclosed, for example, by Topics in Current Chemistry, Vol. 92, pp. 1-44 (1980) and are likewise, as previously quoted, employed in an electro-chromic device in US 4,902,108.
.
~ Among such substances reversibly oxidizable in 2 stages those are preferred which 10 have a uifference of at least 25û mV between their two oxidation states.
The substances which are reversibly oxidizable in two stages are preferably to be understood as those compounds which correspond to one of the formulae (VIII) to (XVIII) R2s ~( R27 R25 ~ ~ R27 ' ~N (Vlll), N~ \R26 R3~ R3s R R 36 15 R~ >=N =~ R34 (X), ~ ~ ~; (Xl) R39 R4' R42 R40 R39 R4' R42 R40 ~ z ~3 (Xll), ~Z 3 (x~
J~ ' 1~ (XIV) ~ >=Z2~< ~ (XV) R~4 E R4s R47 E7 E R49 Le A 31 464-Forei~n Countries Rso Rs4 0 Rs~ N ~, E ~ ~
(XVI), H--N ¦ N--H (XVII), ~E'~~, R53 ~ ss Rs1 0 R
R66 R R Rff9 R70 R7~
~ ~ ~ (XVIII) R~s S ~\ S ) S R
U : -~,~ in which R2s to R25 R3l R32 ~R35 R36 R43 R50 and R51, independently of one another, S represent Cl- to C~8-alkyl, C2- to Cl2-alkenyl, C4- to C7-cycloalkyl, C7- to Cl5-aralkyl or C6- to C~0-aryl, and R43, R50 and R51 may additionally represent hydrogen, R2s R30 R3i R34 R37 R33 R39 to R42 R44 R45 R46 to R49 and R52 to R55, inde-pendently of one another, represent hydrogen, Cl- to C4-afkyl, Cl- to C4-alkoxy, halogen, cyano, nitro, Cl- to C4-alkoxycarbonyl or C6- to C10-aryl, and R54 and R55 additionally represent an aromatic or quasi-aromatic five- or six-membered heterocyclic ring, each of which is option-, ally l" "-~~ f, or a radical of the formulae (V) or (VI), and R45 may ( ¦ ~ additionally represent NR73R74, or R46 and R47 and/or R43 and R49 form a -(CH2)3-, -(CH2)4-, -(CH2)5- or -CH=CH-CH=CH- bndge, zl represents a direct bond, a -CH=CH- or -N--N- bridge, =Z2= lepresents a direct double bond, a =CH-CH= or =N-N= bridge, E3 to E5, El() and El~, independently of one anottler, represent O, S, NRsG or C(C H3)2, and Es may additionally represent C=O or SO2, or r-3 and r4, independently of' one another, additionally represent -CH=CH-, Le A 31 464-Forei~n Countries E6 to E9, b.d~ ly of one another, represent S, Se or NR56~
R56, R73 and R74, hld 1~ Iy of one another, represent Cl- to Cl2-alkyl, C2- to C8-alkenyl, C4- to C7-cycloalkyl, C7- to Cls-aralkyl or C6- to Cl0-aryl, and R73 may additionally represent hydrogen, or NR73R74 represent a five- or six-membered saturated nng which may contain further heteroatoms, R65 to R72, in~ ly of one another, represent hydrogen, Cl- to C6-alkyl, Cl-to C4-alkoxy, cyano, Cl- to C4-alkoxycarbonyl or C6- to Cl0-aryl, and R6s and R66 and R71 and-R77, ind~p~nA~ntly of one another, may additionally ~, ~ form a -(CH2)3-, -(CH2)4- or -CH=CH-CH=CH- bndge, and u represents an integer between 0 and lO.
Preference is given to compounds of the formulae (XIII) to (7~VIII) in which R2s to R28 R3l R32 R35 R36 R43 R50 and Rsl, indl r~ondt ntly of one another, represent C~- to Cl2-alkyl, C2- to C8-alkenyl, cyclohexyl, benzyl or phenyl, and R43, R50 and R5l may additionally represent hydrogen, 29 R30 R33 R34 R37 R38 R39 to R42 R44 R45 R46 to R49 and R52 to Rs, independently of one another, represent hydrogen, methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, cyano, nitro, methoxycarbonyl, ethoxycarbonyl or phenyl, and Rs4 and Rss may additionally represent 2-or 4-pyridyl, or a radical of the formulae (V) or (Vl), and R4s may additionally represent NR73R74, or R46 and R47 and/or R4s and R49 form a -(CH2)3-, -(CI 12)4-, -(CH2)5- or -CH=CH-CH=CH- bridge, Zl represents a direct bond, a -CH=CH- or -N=N- bridge, =Z2= represems a direct double bond, a -CH-CII= or =N-N= bridge, ~5 E3 to Es, El() and Ell, independently of one another, represent O, S or NRs~', and Es may additionally represent C=O, Le A 31 464-Foreign Countries E~' to E9, in~ ly of one another, represent S or Se, Rs6, R73 and R74, independently of one another, represent Cl- to C8-alkyl, C2- to C4-alkenyl, cyclohexyl, benzyl or phenyl, and R73 may additionally repre-sent hydrogen, or NR73R74 represents pyrrolidino, pipendino or morpholi-no, R65, R66, R71 and R72, independently of one another, represent hydrogen, Cl- to C4-alkyl, methu,.yu~l,u--~l, ethu~y~.clbu..~l or phenyl or pairwise form a -(CH2)3- or -(CH2)4- bridge, R67 to R70 represent hydrogen and 10 u represents an integer from O to 6 The elr~ lu~ll.ul,lic system according to the invention preferably comprises at least one couple of oxidizable and reducible substances REDI/OX2, suitable substances OX2 preferably being those of the formulae (1) to (IV) in their general and prefer-red meanings, and suitable substances REDI preferably being those of the 15 formulae (VIII) to (XVIII) in their general and preferred meanings Special preference is given to an electrochromic system comprising a couple REDI/OX2, the substance OX2 being a t~ uli.lh~ salt of formula (I), and the substance RED1 being a compound selected from the group consisting of the for-mulae (VIII), (X), (XI), (XIV) and (XV), in which 20 Rl and R2 correspond to a radical of formula (XIX), R3 corresponds to a radical of formula (XX), R57, Rs9 and R60, independently of one another, represent hydrogen, methyl, ethyl, methoxy, ethoxy, cyano, nitro, -N (CH3)3 or COOH, or Rs7 and R59 jointly form an -O-CI-I,-O- bridge, 25 RsX represents hydrogen, methyl, methoxy or chlorine, Le A 31 464-Forei~n Countries R61 represents methyl, difluoromethyl, I-illuo-u--,cthyl, ' y-,.~ -.yl, ethoxycarbonyl or phenyl, R62 represents hydrogen, methyl, ethyl, phenyl or chlorine, or R61 and R62 together form a -CH=CH-CH=CH- or -CH=CH-C(OCH3)=CH-S bridge, E~2 represents S, X~ represents a colorless anion which is redox-inert under the cobditions, R25 to R2s R3l R32 R35 R36 R43 and R56 represent methyl, ethyl, propyl, butyl, pentyl, hexyl ~or ben2yl, R25 to R2s, R3l and R32, and R3s and R36, respectively, being identical and R43 may additionally represent hydrogen, R29 and R44 represent hydrogen, R4s represents hydrogen, methoxy, ethG,xy, dimethylamino, diethylamino, anilino, N-methylanilino or piperidino, R33 and R34 are identical and represent hydrogen, methyl, methoxy, chlorine, cya-no or methoxycarbonyl, E3 to E5 represent O, S or NR56, but E3 and E4 are identical, , R37 and R3s are identical and represent hydrogen, methyl, ethy~, propyl, butyl or phenyl, zl represents a direct bond or -CH=CH-, R46 to R49 are identical and represent hydrogen, methyl, methoxy, chlorine, cyano, methoxycarbonyl, ethoxycarbonyl or phenyl, Efi to E9 are identical and represent S, Se or NR5~', =Z2= represents a direct double bond, a =CH-CH= or =N-N= bridgc, Rfi5 and R6fi~ and R71 and R72 represent a -(CH2)3- or -(cH2)4- bridge~
CA 02246478 l99X-08-12 Le A 31 464-Foreign Countries R67 to R70 represent hydrogen, and u represents an integer from I to 6.
In a particular c~lllbo.l;lll~, the ele~ ~ ~ system according to the invention, comprises a couple of oxidizable and reducible substances REDI/OX2, REDI and 5 ~X2 being linked via a bridge B, in which B represents a bndge of the formulae -(CH2)n- or -[Yls-(cH2)m-y2]o-(cH2)p-y3q-~
- w. hich may be substituted by Cl- to C4-alkyl, Cl- to C4-alkoxy, halogen. or phenyl, yl to Y3, h~ . nJ. ~Iy of one another, represent O, S, NRs3, COO, CONE~, NHCONE~, cycl.3~ ed;yl~ ~,y~,l. ' ~ ' yl, phenylene or naphthylene, R63 represents Cl- to C6-alkyl, C2- to C6-alkenyl, C4- to C7-cycloalkyl, C7- to Cl5-aralkyl or C6- to C10-aryl, n represents an integer from I to 12, m and p, independently of one another, represent an integer from 0 to 8, 15 o represents an integer from 0 to 6, q and 5, h~ y of one another, represent 0 or 1, and OX2 preferably is a compound of the formulae (I) to (IV), with the general and preferred meanings of the substituents as specified for these formulae and REDI preferably being a compound of the formulae (VIII) to (XVIII) with the 20 general and preferred meanings of the substituents for these formulae, the linkage with the bridge B being effected via the radicals 19 21 R2s R31 R3s R39 R41 R43 R46, R5(), Rs4, R, R, R I R, R, R~'4, R('s or R('(' which in this case constitute a direct bond to the bridge B, or R4~', Rs7 or Rs9 for~ll a sin,,le bond -COO- bridge to the bridge B.
Le A 31 464-Forei~n Countries In the abovementioned meanings of the ~ , alkyl radicals including modifled ones such as e.g. alkoxy or aralkyl radicals are preferably those having from I to 12 C atoms, in particular having from I to 8 C atoms, unless specifiedotherwise. They may be straight-chained or branched and optionally carry further~ such as e.g. Cl- to C4-alkoxy, fluorine, chlorine, hydroxy, cyano, Cl-to C4-alkoxycarbonyl or COOH.
Cycloalkyl radicals are preferably to be understood as those having from 3 to 7 C
atoms, in particular 5 or 6 C atoms.
Alkenyl radicals are preferably those havmg from 2 to 8 C atoms, in particular from 2 to 4 C atoms.
Aryl radicals, includirig those in aralkyl or aroyl radicals, are preferably phenyl or naphthyl radicals, in particular phenyl radicals. They may be substituted by from I
to 3 of the following radicals: Cl- to C6-alkyl, Cl- to C6-alkoxy, fluorine, chlorine, bromine, cyano, hydroxy, Cl- to C6-alku,~y-,a-l,u--yl or nitro. It is also possible for two adjacent radicals to form a ring.
Aromatic or quasi-aromatic five- or six-membered heterocyclic rings, each of which may optionally be benzanellated, refer, in particular, to imidazole, benzimidazole, oxazole, b~ u~d~ulc, thiazole, b~.~uli,;a~ule, indole, pyrazole, triazole, thiophene, isothiazole, benzisothiazole, 1,3,4- or 1,2,4-thiadiazole, 2û pyridine, quinoline, pyrimidine and pyrazine. They may be substituted by from I
, to 3 of the following radicals: Cl- to C6-alkyl, Cl- to C6-alkoxy; fluorine, chlorine, bromine, cyano, nitro, hydroxy, mono- or di-(CI- to C6-alkyl)amino, Cl- to C6-alkoxycarbonyl, Cl- to C6-alkylsulfonyl, Cl- to C6-alkanoylamino, phenyl or naphthyl. It is also possible for tvo adjacent radicals to form a ring.
Tetrazolium salts of formula (I) are disclosed, for example, by Houben-Weyl, Methoden der organischen Chemie, Volume lû/3, p. 685 (1965), EP-A 476,455, EP-A 476,456, EP-A 476,457, naphthotriazolium salts of formula (II) arc disclosed, for examplc, by German Offenlegungsschrift 4,ûû7,û58, cyclopropanes of formula (111) are disclosed for example, by J. Org Chcm 57, 1849 (1992), ll 1.0]bicyclobutanes are disclosed, for example, by J Am. Chem Soc 99, 6120, 6122 (1977) or can be prepared in a manner similar thereto.
Le A 31 464-Foreign Countries The reversibly oxidizable substances i~EDI of formulae (VIII) to (XVIII) are disclosed, for example, by Topics in Current Chemistry, Vol. 92, pp. 1-44 (1980), Angew. Chem. 90, 927 (1978), J. Am. Chem. Soc 117, 8528 (1995), J.C.S. Perkin 11, 1990, 1777 and German orr. " _ irt 4,435,211 or by the 5 literature cited there or can be prepared in a similar manner.
The electrochromic system according to the invention preferably compnses at least one solvent, an ele, ~u~,l.luul;c fluid being produced as a result which is likewise a subject matter of the invention.
. . .
Suitable solvents include ail solvents which are redox-inert under the voltages 10 - selected and which cannot dissociate to form electrophiles or nucleophiles or themselves react as sufficientiy strong electrophiles or nucleophiles and thus could react with the colored ionic free radicais. Examples are propylene carbonate, y-butyrolactone, acetonitrile, propionitrile, glutaronitrile, methylglutaronitrile,
These panes are tllen used to construct a cell by being bonded, preferably 5 cemented, to an annular or rectangular gasket so that their ele~llrJco..du~,Liv~ly coated sides face one another. The gasket establishes a uniform spacing between the panes, for example from 0.1 to 0.5 mm. This cell is then, via a port, filledwith an electrochromic solutioll and is tightly sealed. Via the ITO layer contact can be made separately with the two panes.
I() The prior art cl~ ,.,h.e,----c systems comprise redox couples which, after reduc-tion and oxidation, forrn colored free radicals, cationic free radicals or anionic free radicals, which are chemically reactive. As disclosed, for example, by Topics inCurrent Chemistry, ~ol. 92, pp. 1-44 (1980), such (ionic) free radicals may be sensitive with respect to electrophiles or nucleophiles or even free radicals. To 15 achieve a high stability of an electrochromic device containing such an electro-chromic system which is to survive several thousands of operating cycles it is the-refore necessary to ensure that the solvent used is absolutely free from electrophi-les, e.g. protons, nucleophiles and oxygen. It is also necessary to ensure that such reactive species are not formed by electrochemical processes on the electrodes du-20 ring operation of the electrochromic device.
There was therefore a need for an r;le~ wllic system which comprises at leastone ele~ u~,lu~JI..;c substance which after reduction or oxidation is not converted(. . into an (ionic) free radical species but has a closed electron shell in the reduced or oxidized form.
25 The present invention therefore relates to an electrochromic system comprising at least one oxidizable substance REDI which, by releasing electrons at an anode, is converted from a weakly colored or colorless form into a colored form OXI, and at least one reducible substance OX2 which, by accepting electrons at a cathode, is converted from a weakly colored or colorless form into a colored form RED~, the 30 absorbance in the visible region of the spectrum increasing in each of these cases, and the weakly colored or colorless form being recovered in each case after charge equalization, wherein the reciprocal conversion of oxidized and reduciblc form takes place by a c bond being broken or formed, respectivelyl for at least one of the comprised substances REDI or OX2 Le A 31 464-Foreign Countries Preferably, the cl~ ~ c system according to the invention comprises at least one couple of reducible and oxidizable substances RED,/OX2.
The reduction and oxidation processes in the eleu~,( ' u--uc system according tothe invention generally take place by electrons being accepted or released at a cat-S hode or anode, ~ ,ly, a potenhal difference of from 0.3 to 3 V preferablyobtaining between the electrodes. After the electric potential is switched off, charge equalization generally takes place ~p~ ly between the substances RED2 and OXI, r . ~'1 by bleaching or fading of the color. Such a charge equalization also takes place even while the current is flowing in the interior of 10 . the electrolyte volume.
The cl~ -, ~,.nic system according to the invention preferably comprises, as thereducible substance ~2, a cyclic organic compound which, after accepting I or 2 electrons, is converted~ one of the a bonds of the ring being broken, into an open-ring compound and which, by releasing I or 2 electrons, is converted once more 15 into the cyclic starting compound, in each case precisely two electrons being trans-ferred overall, however.
Said nng opening may take place, for example, by two electrons being accepted directly, resulting in breaking of the bond. Alternatively it is possible for one elec-tron to be accepted initially, whereupon ring opening takes place which may then20 be followed by further reactions such as a further electron and/or a proton being accepted and/or an anionic leaving group being eliminated, precisely 2 electrons(~ , being accepted overall, however. Said ring opening results in an altered 7~ electro system which has a corresponding higher-wavelength and/or higher-absorbance light absorption. Ring closure may correspondingly take place by sllllul~d--~,us25 release of two electrons or ::uccc~ ly by release of first one electron and possi-bly a further electron, and/or the proton which may have been bound is eliminated again and/or the eliminated anionic leaving group is bound once more, precisely 2 electrons being released overall, however T he reducible substance OX2 which is comprised in the electrochromic system 30 according to the invention and comprises, as the reducible subslance OX2 whicll is converted reversibly, a ring a bond being broll;en, into the corresponding open-ring substance RED2, is, in particular, a compound selected from the group consistingof the tetrazolium salts, benzo- or napl~thotria701ium salts, cyclopropanes and ~ CA 02246478 1998-08-12 Le A 31 464-Forei~n Countries [I.l.O]bicyclobutanes. As a result of electrons being accepted and bonds breaking~
the ~,u~ hlg colored compounds from the group consisting of the formazans, amino-azo-benzenes, amino-azo-l, ' ' lc.,~, 1,3-dimethylenepropanes and 1,3-dimethylenecyclobutanes are then formed therefrom.
5 The tetrazolium salts, .- lj ' ' of riSf~olium salts, cyclopropanes and [I.l.O]bicyclobu-tanes are preferably those compounds of the formulae (I) to (IV) + ,R4 R~ R3 N=N
+ N--N (l) ~I~N-Rs N ~ N R6~W
R'9 R16 R8 R" ~( ~<~ (111).R~--R (lv) R7 R12 R~5 Rf in which R1 to Rs, inrl~l....r.'..~lly of one another, represent C6- to C1O-aryl or an aromatic or quasi-aromatic five- or six-membered heterocyclic ring, each of which is optionally bl n7sfnf119f~ f.
R7, R9, Rl3 and Rl4, independently of one another, represent a radical of the formulae (V) to (VII) R2n R21 R20 R21 + N R23 ~/ ~, (V), ~ E E R
Le A 31 464-Forei~n Countries R8, RlS and Rl6, h~ ly of one another, represent C~,- to C1O-aryl, C7-CII-aroyl or a radical of the formulae (V) to (Vll), Rl~ to Rl2, Rl7 and Rl8, h,~ of one another, represent hydrogen, Cl- to C4-alkyl, halogen or cyano, S El and E2, ind~r~nd~ntly of one another, represent O, S or N-RI9, Rl9 and R22, ind~rPnd--ntly of one another, represent Cl- to Cl8-alkyl, C2- to C8-alkenyl, C4- to C7-cycloalkyl, C7- to Cl5-aralkyl or C6- tQ Cl0-aryl, .: R6, R20, R21, R23 and R24, h~ 7 of one another, represent hydrogen, Cl-to C4-alkyl, Cl- to C4-alkoxy, halogen, cyano, nitro or Cl- to C4-alkoxycar-bonyl, or R20 and R21, or R23 and R24, jointly forrn a -CH=CH-CH=CH- bndge, and X~ represents a colorless anion which is redox-inert under the conditions Those compounds of formulae (I) to (IV) are preferred in which Rl to R5, independently of one another, represent a radical of the formulae R58 R 9 R5' ~R57 (XlX), ~ R62 (XXj in wl-ich R'7 to R62, independently of one anothcr, represent hydrooen, Cl- to C6-al-kyl, Cl- to C(,-alkoxy, hydroxy, halo~en, cyano, nitro, di-(CI- to 2Q C4-alkyl)a~ o, tri-(CI- to C4-alkyl)aml11oniul-1, C~- to C6-alkanoy-lamino, benzoylamhlo, Cl- to C~,-alkyl-sulfonylamino, benzenesul~o-nylamino, Cl- to C4-alkoxycarbonyl or COOH, or Le A 31 464-Forei~n Countries radicals juxtaposed in pairs jointly form an -O-(CH2)2 3-, -O-(CH2)1 2-O-, -NR63-(CH2)2 3- or -NR53-(CH2)1 2-o- bridge, or R58 and R59 and/or R61 and R62 form a -CH=CH-CH=CH- bridge which may be substituted by methyl, methoxy or chlorine, S R63 represents hydrogen or C1- to C4-alkyl, E12 represents O, S or NR6q, R64 represents hydrogen, C1- to Cl8-alkyl, C2- to C12-alkenyl, C4- to C7-cy cloalkyl, C7- to C15-arallyl or C6- to C10-aryl, R7, R9, R13 and Rl4 represent a radical of formula (V) and are pairwise identical, R8, Rl5 and Rl6 represent phenyl or a radical of formula (V), and R~5 and Rl6 are identical, R6, Rl~ and R12 represent hydrogen, Rl 1 represents hydrogen, methyl, cyano or chlorine, Rl7 and Rl8 represent hydrogen or methyl and are identical, . 15 E1 represents O or NR19, R19 represents C1- to Cl2-alkyl, C2- to C4-alkenyl, cyclohexyl, benzyl or phenyl, R20 and R21 represent hydrogen or jointly form a -CH=CII-CH=CH- bridge, and X~ represents a colorless anion which is redox-inert under the conditions.
The electrochromic system according to the invention, whicll prcferably comprises, as oxidizable substances REDI, those organic compounds which are able to release Le A 31 464-Foreign Countries 2 electrons reversibly in two stages, a higher...~ ,th and/or stronger light absorption being achieved, in particular, after one electron has been released.
In a cyclic voltamn ogram, recorded in an inert solvent, these substances RFDI
exhibit at least 2, as a rule precisely 2, clc~ u~,l.~,.l-ically and chemically reversible S oxidation states which are each caused by an electron being released. Such sub-stances are disclosed, for example, by Topics in Current Chemistry, Vol. 92, pp. 1-44 (1980) and are likewise, as previously quoted, employed in an electro-chromic device in US 4,902,108.
.
~ Among such substances reversibly oxidizable in 2 stages those are preferred which 10 have a uifference of at least 25û mV between their two oxidation states.
The substances which are reversibly oxidizable in two stages are preferably to be understood as those compounds which correspond to one of the formulae (VIII) to (XVIII) R2s ~( R27 R25 ~ ~ R27 ' ~N (Vlll), N~ \R26 R3~ R3s R R 36 15 R~ >=N =~ R34 (X), ~ ~ ~; (Xl) R39 R4' R42 R40 R39 R4' R42 R40 ~ z ~3 (Xll), ~Z 3 (x~
J~ ' 1~ (XIV) ~ >=Z2~< ~ (XV) R~4 E R4s R47 E7 E R49 Le A 31 464-Forei~n Countries Rso Rs4 0 Rs~ N ~, E ~ ~
(XVI), H--N ¦ N--H (XVII), ~E'~~, R53 ~ ss Rs1 0 R
R66 R R Rff9 R70 R7~
~ ~ ~ (XVIII) R~s S ~\ S ) S R
U : -~,~ in which R2s to R25 R3l R32 ~R35 R36 R43 R50 and R51, independently of one another, S represent Cl- to C~8-alkyl, C2- to Cl2-alkenyl, C4- to C7-cycloalkyl, C7- to Cl5-aralkyl or C6- to C~0-aryl, and R43, R50 and R51 may additionally represent hydrogen, R2s R30 R3i R34 R37 R33 R39 to R42 R44 R45 R46 to R49 and R52 to R55, inde-pendently of one another, represent hydrogen, Cl- to C4-afkyl, Cl- to C4-alkoxy, halogen, cyano, nitro, Cl- to C4-alkoxycarbonyl or C6- to C10-aryl, and R54 and R55 additionally represent an aromatic or quasi-aromatic five- or six-membered heterocyclic ring, each of which is option-, ally l" "-~~ f, or a radical of the formulae (V) or (VI), and R45 may ( ¦ ~ additionally represent NR73R74, or R46 and R47 and/or R43 and R49 form a -(CH2)3-, -(CH2)4-, -(CH2)5- or -CH=CH-CH=CH- bndge, zl represents a direct bond, a -CH=CH- or -N--N- bridge, =Z2= lepresents a direct double bond, a =CH-CH= or =N-N= bridge, E3 to E5, El() and El~, independently of one anottler, represent O, S, NRsG or C(C H3)2, and Es may additionally represent C=O or SO2, or r-3 and r4, independently of' one another, additionally represent -CH=CH-, Le A 31 464-Forei~n Countries E6 to E9, b.d~ ly of one another, represent S, Se or NR56~
R56, R73 and R74, hld 1~ Iy of one another, represent Cl- to Cl2-alkyl, C2- to C8-alkenyl, C4- to C7-cycloalkyl, C7- to Cls-aralkyl or C6- to Cl0-aryl, and R73 may additionally represent hydrogen, or NR73R74 represent a five- or six-membered saturated nng which may contain further heteroatoms, R65 to R72, in~ ly of one another, represent hydrogen, Cl- to C6-alkyl, Cl-to C4-alkoxy, cyano, Cl- to C4-alkoxycarbonyl or C6- to Cl0-aryl, and R6s and R66 and R71 and-R77, ind~p~nA~ntly of one another, may additionally ~, ~ form a -(CH2)3-, -(CH2)4- or -CH=CH-CH=CH- bndge, and u represents an integer between 0 and lO.
Preference is given to compounds of the formulae (XIII) to (7~VIII) in which R2s to R28 R3l R32 R35 R36 R43 R50 and Rsl, indl r~ondt ntly of one another, represent C~- to Cl2-alkyl, C2- to C8-alkenyl, cyclohexyl, benzyl or phenyl, and R43, R50 and R5l may additionally represent hydrogen, 29 R30 R33 R34 R37 R38 R39 to R42 R44 R45 R46 to R49 and R52 to Rs, independently of one another, represent hydrogen, methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, cyano, nitro, methoxycarbonyl, ethoxycarbonyl or phenyl, and Rs4 and Rss may additionally represent 2-or 4-pyridyl, or a radical of the formulae (V) or (Vl), and R4s may additionally represent NR73R74, or R46 and R47 and/or R4s and R49 form a -(CH2)3-, -(CI 12)4-, -(CH2)5- or -CH=CH-CH=CH- bridge, Zl represents a direct bond, a -CH=CH- or -N=N- bridge, =Z2= represems a direct double bond, a -CH-CII= or =N-N= bridge, ~5 E3 to Es, El() and Ell, independently of one another, represent O, S or NRs~', and Es may additionally represent C=O, Le A 31 464-Foreign Countries E~' to E9, in~ ly of one another, represent S or Se, Rs6, R73 and R74, independently of one another, represent Cl- to C8-alkyl, C2- to C4-alkenyl, cyclohexyl, benzyl or phenyl, and R73 may additionally repre-sent hydrogen, or NR73R74 represents pyrrolidino, pipendino or morpholi-no, R65, R66, R71 and R72, independently of one another, represent hydrogen, Cl- to C4-alkyl, methu,.yu~l,u--~l, ethu~y~.clbu..~l or phenyl or pairwise form a -(CH2)3- or -(CH2)4- bridge, R67 to R70 represent hydrogen and 10 u represents an integer from O to 6 The elr~ lu~ll.ul,lic system according to the invention preferably comprises at least one couple of oxidizable and reducible substances REDI/OX2, suitable substances OX2 preferably being those of the formulae (1) to (IV) in their general and prefer-red meanings, and suitable substances REDI preferably being those of the 15 formulae (VIII) to (XVIII) in their general and preferred meanings Special preference is given to an electrochromic system comprising a couple REDI/OX2, the substance OX2 being a t~ uli.lh~ salt of formula (I), and the substance RED1 being a compound selected from the group consisting of the for-mulae (VIII), (X), (XI), (XIV) and (XV), in which 20 Rl and R2 correspond to a radical of formula (XIX), R3 corresponds to a radical of formula (XX), R57, Rs9 and R60, independently of one another, represent hydrogen, methyl, ethyl, methoxy, ethoxy, cyano, nitro, -N (CH3)3 or COOH, or Rs7 and R59 jointly form an -O-CI-I,-O- bridge, 25 RsX represents hydrogen, methyl, methoxy or chlorine, Le A 31 464-Forei~n Countries R61 represents methyl, difluoromethyl, I-illuo-u--,cthyl, ' y-,.~ -.yl, ethoxycarbonyl or phenyl, R62 represents hydrogen, methyl, ethyl, phenyl or chlorine, or R61 and R62 together form a -CH=CH-CH=CH- or -CH=CH-C(OCH3)=CH-S bridge, E~2 represents S, X~ represents a colorless anion which is redox-inert under the cobditions, R25 to R2s R3l R32 R35 R36 R43 and R56 represent methyl, ethyl, propyl, butyl, pentyl, hexyl ~or ben2yl, R25 to R2s, R3l and R32, and R3s and R36, respectively, being identical and R43 may additionally represent hydrogen, R29 and R44 represent hydrogen, R4s represents hydrogen, methoxy, ethG,xy, dimethylamino, diethylamino, anilino, N-methylanilino or piperidino, R33 and R34 are identical and represent hydrogen, methyl, methoxy, chlorine, cya-no or methoxycarbonyl, E3 to E5 represent O, S or NR56, but E3 and E4 are identical, , R37 and R3s are identical and represent hydrogen, methyl, ethy~, propyl, butyl or phenyl, zl represents a direct bond or -CH=CH-, R46 to R49 are identical and represent hydrogen, methyl, methoxy, chlorine, cyano, methoxycarbonyl, ethoxycarbonyl or phenyl, Efi to E9 are identical and represent S, Se or NR5~', =Z2= represents a direct double bond, a =CH-CH= or =N-N= bridgc, Rfi5 and R6fi~ and R71 and R72 represent a -(CH2)3- or -(cH2)4- bridge~
CA 02246478 l99X-08-12 Le A 31 464-Foreign Countries R67 to R70 represent hydrogen, and u represents an integer from I to 6.
In a particular c~lllbo.l;lll~, the ele~ ~ ~ system according to the invention, comprises a couple of oxidizable and reducible substances REDI/OX2, REDI and 5 ~X2 being linked via a bridge B, in which B represents a bndge of the formulae -(CH2)n- or -[Yls-(cH2)m-y2]o-(cH2)p-y3q-~
- w. hich may be substituted by Cl- to C4-alkyl, Cl- to C4-alkoxy, halogen. or phenyl, yl to Y3, h~ . nJ. ~Iy of one another, represent O, S, NRs3, COO, CONE~, NHCONE~, cycl.3~ ed;yl~ ~,y~,l. ' ~ ' yl, phenylene or naphthylene, R63 represents Cl- to C6-alkyl, C2- to C6-alkenyl, C4- to C7-cycloalkyl, C7- to Cl5-aralkyl or C6- to C10-aryl, n represents an integer from I to 12, m and p, independently of one another, represent an integer from 0 to 8, 15 o represents an integer from 0 to 6, q and 5, h~ y of one another, represent 0 or 1, and OX2 preferably is a compound of the formulae (I) to (IV), with the general and preferred meanings of the substituents as specified for these formulae and REDI preferably being a compound of the formulae (VIII) to (XVIII) with the 20 general and preferred meanings of the substituents for these formulae, the linkage with the bridge B being effected via the radicals 19 21 R2s R31 R3s R39 R41 R43 R46, R5(), Rs4, R, R, R I R, R, R~'4, R('s or R('(' which in this case constitute a direct bond to the bridge B, or R4~', Rs7 or Rs9 for~ll a sin,,le bond -COO- bridge to the bridge B.
Le A 31 464-Forei~n Countries In the abovementioned meanings of the ~ , alkyl radicals including modifled ones such as e.g. alkoxy or aralkyl radicals are preferably those having from I to 12 C atoms, in particular having from I to 8 C atoms, unless specifiedotherwise. They may be straight-chained or branched and optionally carry further~ such as e.g. Cl- to C4-alkoxy, fluorine, chlorine, hydroxy, cyano, Cl-to C4-alkoxycarbonyl or COOH.
Cycloalkyl radicals are preferably to be understood as those having from 3 to 7 C
atoms, in particular 5 or 6 C atoms.
Alkenyl radicals are preferably those havmg from 2 to 8 C atoms, in particular from 2 to 4 C atoms.
Aryl radicals, includirig those in aralkyl or aroyl radicals, are preferably phenyl or naphthyl radicals, in particular phenyl radicals. They may be substituted by from I
to 3 of the following radicals: Cl- to C6-alkyl, Cl- to C6-alkoxy, fluorine, chlorine, bromine, cyano, hydroxy, Cl- to C6-alku,~y-,a-l,u--yl or nitro. It is also possible for two adjacent radicals to form a ring.
Aromatic or quasi-aromatic five- or six-membered heterocyclic rings, each of which may optionally be benzanellated, refer, in particular, to imidazole, benzimidazole, oxazole, b~ u~d~ulc, thiazole, b~.~uli,;a~ule, indole, pyrazole, triazole, thiophene, isothiazole, benzisothiazole, 1,3,4- or 1,2,4-thiadiazole, 2û pyridine, quinoline, pyrimidine and pyrazine. They may be substituted by from I
, to 3 of the following radicals: Cl- to C6-alkyl, Cl- to C6-alkoxy; fluorine, chlorine, bromine, cyano, nitro, hydroxy, mono- or di-(CI- to C6-alkyl)amino, Cl- to C6-alkoxycarbonyl, Cl- to C6-alkylsulfonyl, Cl- to C6-alkanoylamino, phenyl or naphthyl. It is also possible for tvo adjacent radicals to form a ring.
Tetrazolium salts of formula (I) are disclosed, for example, by Houben-Weyl, Methoden der organischen Chemie, Volume lû/3, p. 685 (1965), EP-A 476,455, EP-A 476,456, EP-A 476,457, naphthotriazolium salts of formula (II) arc disclosed, for examplc, by German Offenlegungsschrift 4,ûû7,û58, cyclopropanes of formula (111) are disclosed for example, by J. Org Chcm 57, 1849 (1992), ll 1.0]bicyclobutanes are disclosed, for example, by J Am. Chem Soc 99, 6120, 6122 (1977) or can be prepared in a manner similar thereto.
Le A 31 464-Foreign Countries The reversibly oxidizable substances i~EDI of formulae (VIII) to (XVIII) are disclosed, for example, by Topics in Current Chemistry, Vol. 92, pp. 1-44 (1980), Angew. Chem. 90, 927 (1978), J. Am. Chem. Soc 117, 8528 (1995), J.C.S. Perkin 11, 1990, 1777 and German orr. " _ irt 4,435,211 or by the 5 literature cited there or can be prepared in a similar manner.
The electrochromic system according to the invention preferably compnses at least one solvent, an ele, ~u~,l.luul;c fluid being produced as a result which is likewise a subject matter of the invention.
. . .
Suitable solvents include ail solvents which are redox-inert under the voltages 10 - selected and which cannot dissociate to form electrophiles or nucleophiles or themselves react as sufficientiy strong electrophiles or nucleophiles and thus could react with the colored ionic free radicais. Examples are propylene carbonate, y-butyrolactone, acetonitrile, propionitrile, glutaronitrile, methylglutaronitrile,
3,3'-oxydipropionitrile, hydroxypropionitrile, dimethylformamide, N-methyl-15 pyrrolidone, sulfolane, 3-methylsulfolane c~r mixtures thereof. Preferred arepropylene carbonate and mixtures thereof with glutaronitrile or 3-methylsulfolane.
The electrochromic fluid according to the invention may contain at least one inert conducting sait Suitable inert conducting salts include lithium salts, sodium salts and tetraalkylam-20 monium salts, in particuiar the latter. The aikyl groups may have from 1 to 18 C
atoms and may be identical or different. Preference is given to tetrabutyl-ammonium. Anions suitable for these salts but also as anions X~ in the formulae (I), (II), (IV), (VI), (VII) include all redox-inert, colorless anions.Examples are tetrafluoroborate, perchlorate, methanesulfonate, trifluoro-25 methanesulfonate, perfluorobutanesulfonate, benzenesulfonate, hexafluorophos-phate, hexafluoroarsenate and hexafluorosilicate. In the latter case, X~ represents 1/2 Si~62-.
The conducting salts are employed. for examplc, in the range of frorn 0 to I
molar 30 Further additives to the ele-.L,u~l"u,ll-c fluid may include thickeners~ to control tl~e viscosity ot' the tluid l'his may matter in avoiding scgregatiolll i e the forlllatioll Le A 31 464-Forei jln Countries of stripy or patchy coloration upon prolonged operation of an energized electrochromic device containing the electrochromic fluid according to the invention, and for controlling the bleaching rate once the current has been switched off 5 Suitable thickeners include all compounds customary for these purposes, such as e.g. pulya~lyhlt~ uly~ ,Ll-~wy'~~~ (Luctile L~), ,uuly~,~br ' and polyurethane.
The ele~ u~ Llu-l-;c fluid may also be in the form of a gel.
.
. Suitable further additives for the el~-,t u~,LIul~;c fluid include UV absorbers to improve the lightfrc~n~ cc Examples are WINUL~ 3000 (2,4-dihydroxybenzo-phenone, BASF), SANDUVOR~ 3035 (2-hydroxy-4-n-octyloxybl rl ~rle, Clariant), Tinuvin~571 (Z-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, Ciba), Cyasorb 24TM (2,2'-dihydroxy-4-methoxybenzophenone, American Cyanamid Company), UVINUL~ 3035 (ethyl 2-cyano-3,3-diphenylacrylate, BASF), UVINUL~ 3039 (2-ethylhexyl 2-cyano-3,3-diphenylacrylate, BASF), WINULJ 3088 (2-ethylhexyl p-methoxycinnamate, BASF).
The W absorbers are employed in the range of from 0.01 to 2 mol/l, preferably from 0.04 to I mol/l.
The el~ u~,l..umic fluid contains each of the electrochromic substances OX2 and REDI, in particular those of the formulae (I) to (IV) and (VIII) to (XVIII), in a , 20 concentration of at least 104 mol/l, preferably from 0.001 to 0.. 5 mol/l. The totai concentrahon of all the ch,~,t-u~,l..u---;c substances present is preferably below I mol/l.
R~DI and OX2 are employed in the ratio of from 1:3 to 3:1, preferably from 1:1 to 1:2.
25 The electrochromic fluids according to the invention are eminently suitable as a component of an electrochromic device I he present invention thercfore further relates to electrochrol1lic devices containing an electrochromic fluid according to the invention The design of an electrochromic device whicll may be configured~
c.g.l as a window pane, car canopy, car rearview mirror or display, is known in 30 principle T he electrochromic device according to the invention comprises two Le A 31 464-Forei~n Countries transparent glass or plastic panes which face one another, one of which is optionally mirrored and whose sides which face one another are coated electroconductively, e.g. with indium tin oxide (ITO), between which the elc~ ic fluid according to the invention is located. Other conductive 5 materials are likewise suitable: bn oxide, tin oxide doped with antimony or fluorine, zinc oxide doped with antimony or aluminum. Conductive organic polymers such as polythienyls, polypyrroles, luoly lin~c, polyacetylene, each ofwhich is optionally substituted, are likewise suitable. If one of the panes is mirrored, it may likewise be utilized as a conductive layer. The spacing of the two panes is. generally 0.005-2 mm, prefer.ably 0.2-0.5 mm. .The desired spacing between the panes is generally established by means of a gasket.
In addition to the above-described substances REDp OX2, the ele~,L~u~ l.;c system according to t4e invention may also contain others such as those described, for example, in US 4,902,108, Topics in Current Chemistry, Vol. 92, pp. 1-44 (1980) and Angew. Chem. 90, 927 (1978). Reference is made to those in particu-lar which may be converted reversibly, by reduction, into a colored for n. Such electrochromic substances stem, for example, from the groups of the viologens and the redox systems related thereto, which have quaternized quasi-aromatic five-membered rings as end systems, p-di ~ ~ n~ es and diaminobiphenyls, 20 quinones, quinone imines and rlninorlirn~th~nl~c An admixture of such redox systems may be advantageous, for example, to correct the hue of e.g the display,when energized, in the case of the el~,t.o~,lll~,..lic device according to the invention.
( .
ExamPles 25 Example I
A display cell like that described in US 4,902,108 in Examples I to 3 was constructed from two glass plates coated with indiun- tin oxide (ITO) and a gasket Via a port in the gasket it was filled with a solution of tetraaolium salt (0.025 molar) of formula Le A 31 464-Porei~n Countries Cl~ ~
N--N
N~N BF~ QO(I) ~ O
ol ~tldth;drulv~iene (0.025 molar) of the formula - -S S
- ~ ~ 3 (~
~ s S
and tetrabutyl~mmoninm tetrafluoroborate (0.5 molar) in anhydrous propylene 5 carbonate The color of the solution in the cell was pale yellow. After a voltage of 1.5 V was applied, the solution rapidly turned deep red, after the power supply was switched off the cell contents bleached once more within about 30 s, resulting in the original pale yellow. More than 100 such operating cycles were survived without any changes.
10 If the one glass pane was silvered opposite its ITO-coated side, a mirror was obtained which could be darkened.
Example 2 A display cell as in Example I was constructed. It was filled with a solution oftetrazolium salt (0.025 molar) of formula (XXI), (see Example 1), N-methyl-15 phenothiazine (0.025 molar) of formula ~ (XXIII) Le A 31 464-Foreign Countries and ~tldlJui)/' ~ ol,~,ld~e (0.5 molar) in anhydrous propylene carbonate. The color of the solution in the cell was pale yellow. After a voltage of 1.5 V was applied, the solution rapidly turned deep bluish-red, after the power supply was switched off the cell contents bleached once more within about 30 s, S resulting in the original pale yellow. More than 100 such operating cycles were survived without any changes.
Example 3 A display cell as In Example I was constructed. Beforehand, however, as - - descnbed in US 4,902,108, Exarnpie 10, one of the glass plates was coated, on the 10 ITO-coated side, with a solutioll of a polyacrylate and the solvent was evaporated.
Then the cell was filled with a solution of tetrazolium salt (0.017 molar) of formula ~ OCH3~0CH3 H3C ~ ~OCH3 + N--N
N~N NO3 (XXIV), ~S
N-butylp~ ~thi~7inl~ (0.033 molar) of formula I S ~N~[3 C4Hg and tetrabutylammonium tetrafluoroborate (0.5 molar) in a 4:2 mixture of anhydrous propylene carbonate and anhydrous glutaronitrile via a port m the gasket The solution thickened by the polyacrylate was yellow witll a slight green cast After a voltagc of 1.5 V was applied, it lapidly turned red-brown After thc20 voltage was switched off, the solutlon bleached again. Shorting the cell accelerated ~ CA 02246478 1998-08-12 Le A 31 464-Forei~n Countries the bleaching process More than 100 such operating cycles were survived without any changes.
Example 4 A display cell as in Example I was constructed It was filled with a solution of 5 tetrazolium salt (0 025 molar) of formula - CHF~ oCH3 oCH3 ~N I)=~OCH --~- 3 Q(X,vl).
+ N--N
N~N 13 S03-o~o N-methylphenothiazine (0.025 molar) of formula (XXIII) (see Example 2) and tetrabutylammonium tetrafluoroborate (0 5 molar) in anhydrous propylene carbonate. The color of the solution in the cell was pale yellow After a voltage of 10 1 5 V was applied, the solution rapidly turned deep red, after the power supply was switched off the cell contents bleached once more within about 30 s, resulting in the original pale yellow. More than 100 such operating cycles were survived without any changes After I h of continuous operation in the energized state, operation of the display was unaffected.
15 In an entirely similar manner, employing the following electrochromic substances listed in the table, cle~,~u~ .,ic display cells were constructed and similarly good results were achieved ~ CA 02246478 1998-08-12 LeA31464-Forei~nCountries Ta~le 1~\ OXz REDI Color S CF3 S S purplc = N - N =<
N~N 13F<~
~\o ", o _/ .
i~
6 N S S black-purple N - N, S ~3 [~ >~ N--N =< ~13 ~N l~HF 1<H~
7 ~ ,NO2 [~ purplc N[~N CH3 CH3 813, oc~, CH3 l H3 red ~5 N--NJ~ ~--N~<N ~
F F S S--V
~' Le A 31 464-Forei~n Countries Ex. OX2 REDI Color g OC H, CH3 CH3 purple NO, ' . ' , . ' . . .
0 ~ 3 ~ blue l l OCH, C2Hs red F,C ~ N ~ OCH, CIJ~S N--NJ~O H, NO, O
NHCOaH, 12 N--~N ~CH CH3 CH3 CH3 gre~n = N N
SF~lH3 CH3 Le A 31 464-Foreign Countries Ex OX2 REDI Color 13 NC~ ~NO, ~S S red N N S s 3 PF~
The electrochromic fluid according to the invention may contain at least one inert conducting sait Suitable inert conducting salts include lithium salts, sodium salts and tetraalkylam-20 monium salts, in particuiar the latter. The aikyl groups may have from 1 to 18 C
atoms and may be identical or different. Preference is given to tetrabutyl-ammonium. Anions suitable for these salts but also as anions X~ in the formulae (I), (II), (IV), (VI), (VII) include all redox-inert, colorless anions.Examples are tetrafluoroborate, perchlorate, methanesulfonate, trifluoro-25 methanesulfonate, perfluorobutanesulfonate, benzenesulfonate, hexafluorophos-phate, hexafluoroarsenate and hexafluorosilicate. In the latter case, X~ represents 1/2 Si~62-.
The conducting salts are employed. for examplc, in the range of frorn 0 to I
molar 30 Further additives to the ele-.L,u~l"u,ll-c fluid may include thickeners~ to control tl~e viscosity ot' the tluid l'his may matter in avoiding scgregatiolll i e the forlllatioll Le A 31 464-Forei jln Countries of stripy or patchy coloration upon prolonged operation of an energized electrochromic device containing the electrochromic fluid according to the invention, and for controlling the bleaching rate once the current has been switched off 5 Suitable thickeners include all compounds customary for these purposes, such as e.g. pulya~lyhlt~ uly~ ,Ll-~wy'~~~ (Luctile L~), ,uuly~,~br ' and polyurethane.
The ele~ u~ Llu-l-;c fluid may also be in the form of a gel.
.
. Suitable further additives for the el~-,t u~,LIul~;c fluid include UV absorbers to improve the lightfrc~n~ cc Examples are WINUL~ 3000 (2,4-dihydroxybenzo-phenone, BASF), SANDUVOR~ 3035 (2-hydroxy-4-n-octyloxybl rl ~rle, Clariant), Tinuvin~571 (Z-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, Ciba), Cyasorb 24TM (2,2'-dihydroxy-4-methoxybenzophenone, American Cyanamid Company), UVINUL~ 3035 (ethyl 2-cyano-3,3-diphenylacrylate, BASF), UVINUL~ 3039 (2-ethylhexyl 2-cyano-3,3-diphenylacrylate, BASF), WINULJ 3088 (2-ethylhexyl p-methoxycinnamate, BASF).
The W absorbers are employed in the range of from 0.01 to 2 mol/l, preferably from 0.04 to I mol/l.
The el~ u~,l..umic fluid contains each of the electrochromic substances OX2 and REDI, in particular those of the formulae (I) to (IV) and (VIII) to (XVIII), in a , 20 concentration of at least 104 mol/l, preferably from 0.001 to 0.. 5 mol/l. The totai concentrahon of all the ch,~,t-u~,l..u---;c substances present is preferably below I mol/l.
R~DI and OX2 are employed in the ratio of from 1:3 to 3:1, preferably from 1:1 to 1:2.
25 The electrochromic fluids according to the invention are eminently suitable as a component of an electrochromic device I he present invention thercfore further relates to electrochrol1lic devices containing an electrochromic fluid according to the invention The design of an electrochromic device whicll may be configured~
c.g.l as a window pane, car canopy, car rearview mirror or display, is known in 30 principle T he electrochromic device according to the invention comprises two Le A 31 464-Forei~n Countries transparent glass or plastic panes which face one another, one of which is optionally mirrored and whose sides which face one another are coated electroconductively, e.g. with indium tin oxide (ITO), between which the elc~ ic fluid according to the invention is located. Other conductive 5 materials are likewise suitable: bn oxide, tin oxide doped with antimony or fluorine, zinc oxide doped with antimony or aluminum. Conductive organic polymers such as polythienyls, polypyrroles, luoly lin~c, polyacetylene, each ofwhich is optionally substituted, are likewise suitable. If one of the panes is mirrored, it may likewise be utilized as a conductive layer. The spacing of the two panes is. generally 0.005-2 mm, prefer.ably 0.2-0.5 mm. .The desired spacing between the panes is generally established by means of a gasket.
In addition to the above-described substances REDp OX2, the ele~,L~u~ l.;c system according to t4e invention may also contain others such as those described, for example, in US 4,902,108, Topics in Current Chemistry, Vol. 92, pp. 1-44 (1980) and Angew. Chem. 90, 927 (1978). Reference is made to those in particu-lar which may be converted reversibly, by reduction, into a colored for n. Such electrochromic substances stem, for example, from the groups of the viologens and the redox systems related thereto, which have quaternized quasi-aromatic five-membered rings as end systems, p-di ~ ~ n~ es and diaminobiphenyls, 20 quinones, quinone imines and rlninorlirn~th~nl~c An admixture of such redox systems may be advantageous, for example, to correct the hue of e.g the display,when energized, in the case of the el~,t.o~,lll~,..lic device according to the invention.
( .
ExamPles 25 Example I
A display cell like that described in US 4,902,108 in Examples I to 3 was constructed from two glass plates coated with indiun- tin oxide (ITO) and a gasket Via a port in the gasket it was filled with a solution of tetraaolium salt (0.025 molar) of formula Le A 31 464-Porei~n Countries Cl~ ~
N--N
N~N BF~ QO(I) ~ O
ol ~tldth;drulv~iene (0.025 molar) of the formula - -S S
- ~ ~ 3 (~
~ s S
and tetrabutyl~mmoninm tetrafluoroborate (0.5 molar) in anhydrous propylene 5 carbonate The color of the solution in the cell was pale yellow. After a voltage of 1.5 V was applied, the solution rapidly turned deep red, after the power supply was switched off the cell contents bleached once more within about 30 s, resulting in the original pale yellow. More than 100 such operating cycles were survived without any changes.
10 If the one glass pane was silvered opposite its ITO-coated side, a mirror was obtained which could be darkened.
Example 2 A display cell as in Example I was constructed. It was filled with a solution oftetrazolium salt (0.025 molar) of formula (XXI), (see Example 1), N-methyl-15 phenothiazine (0.025 molar) of formula ~ (XXIII) Le A 31 464-Foreign Countries and ~tldlJui)/' ~ ol,~,ld~e (0.5 molar) in anhydrous propylene carbonate. The color of the solution in the cell was pale yellow. After a voltage of 1.5 V was applied, the solution rapidly turned deep bluish-red, after the power supply was switched off the cell contents bleached once more within about 30 s, S resulting in the original pale yellow. More than 100 such operating cycles were survived without any changes.
Example 3 A display cell as In Example I was constructed. Beforehand, however, as - - descnbed in US 4,902,108, Exarnpie 10, one of the glass plates was coated, on the 10 ITO-coated side, with a solutioll of a polyacrylate and the solvent was evaporated.
Then the cell was filled with a solution of tetrazolium salt (0.017 molar) of formula ~ OCH3~0CH3 H3C ~ ~OCH3 + N--N
N~N NO3 (XXIV), ~S
N-butylp~ ~thi~7inl~ (0.033 molar) of formula I S ~N~[3 C4Hg and tetrabutylammonium tetrafluoroborate (0.5 molar) in a 4:2 mixture of anhydrous propylene carbonate and anhydrous glutaronitrile via a port m the gasket The solution thickened by the polyacrylate was yellow witll a slight green cast After a voltagc of 1.5 V was applied, it lapidly turned red-brown After thc20 voltage was switched off, the solutlon bleached again. Shorting the cell accelerated ~ CA 02246478 1998-08-12 Le A 31 464-Forei~n Countries the bleaching process More than 100 such operating cycles were survived without any changes.
Example 4 A display cell as in Example I was constructed It was filled with a solution of 5 tetrazolium salt (0 025 molar) of formula - CHF~ oCH3 oCH3 ~N I)=~OCH --~- 3 Q(X,vl).
+ N--N
N~N 13 S03-o~o N-methylphenothiazine (0.025 molar) of formula (XXIII) (see Example 2) and tetrabutylammonium tetrafluoroborate (0 5 molar) in anhydrous propylene carbonate. The color of the solution in the cell was pale yellow After a voltage of 10 1 5 V was applied, the solution rapidly turned deep red, after the power supply was switched off the cell contents bleached once more within about 30 s, resulting in the original pale yellow. More than 100 such operating cycles were survived without any changes After I h of continuous operation in the energized state, operation of the display was unaffected.
15 In an entirely similar manner, employing the following electrochromic substances listed in the table, cle~,~u~ .,ic display cells were constructed and similarly good results were achieved ~ CA 02246478 1998-08-12 LeA31464-Forei~nCountries Ta~le 1~\ OXz REDI Color S CF3 S S purplc = N - N =<
N~N 13F<~
~\o ", o _/ .
i~
6 N S S black-purple N - N, S ~3 [~ >~ N--N =< ~13 ~N l~HF 1<H~
7 ~ ,NO2 [~ purplc N[~N CH3 CH3 813, oc~, CH3 l H3 red ~5 N--NJ~ ~--N~<N ~
F F S S--V
~' Le A 31 464-Forei~n Countries Ex. OX2 REDI Color g OC H, CH3 CH3 purple NO, ' . ' , . ' . . .
0 ~ 3 ~ blue l l OCH, C2Hs red F,C ~ N ~ OCH, CIJ~S N--NJ~O H, NO, O
NHCOaH, 12 N--~N ~CH CH3 CH3 CH3 gre~n = N N
SF~lH3 CH3 Le A 31 464-Foreign Countries Ex OX2 REDI Color 13 NC~ ~NO, ~S S red N N S s 3 PF~
4 ' C11~ CH, purple CO~CH3--~N=N ~CH3 N N
[ o~Jo ,~, CH30CO S S COOCH3 led \~ N(CH,~
N--NJ~ CH30CO COOCH3 N~fN
2 BF~
Oa1, IG ~ ~ ~cO~ CH~ purple c~ c~lso~3 CH3 Se CH3 Le A 31 464-Forei~n Countries Ex. OX2 REDI Color 1 7 ~N ~OC,H~ H purple ~C~.
r~, - . ~33~ ~N~3 red ~s~ ~ r~F~ ~
19 0,N~[~ ,OCH, NC S S~CN red CH, CH, N~J~ j ~N--CH, ICH3 blue-green 1~ 2 C104 ~ ~3 LeA31464-Forei~nCountnes Ex OX2 REDI Color C H--~ ~ j C~H~ 3 purple 22 G' "' .~7~ 3 [~5~3 purplc N
C,H j 23 ~CH, I~N~1 purple CH, N~N--CH, CH, ~/ 2 BF4 24 coo--(CH2), N S
CH, S ~--N--N
~ ~
[ o~Jo ,~, CH30CO S S COOCH3 led \~ N(CH,~
N--NJ~ CH30CO COOCH3 N~fN
2 BF~
Oa1, IG ~ ~ ~cO~ CH~ purple c~ c~lso~3 CH3 Se CH3 Le A 31 464-Forei~n Countries Ex. OX2 REDI Color 1 7 ~N ~OC,H~ H purple ~C~.
r~, - . ~33~ ~N~3 red ~s~ ~ r~F~ ~
19 0,N~[~ ,OCH, NC S S~CN red CH, CH, N~J~ j ~N--CH, ICH3 blue-green 1~ 2 C104 ~ ~3 LeA31464-Forei~nCountnes Ex OX2 REDI Color C H--~ ~ j C~H~ 3 purple 22 G' "' .~7~ 3 [~5~3 purplc N
C,H j 23 ~CH, I~N~1 purple CH, N~N--CH, CH, ~/ 2 BF4 24 coo--(CH2), N S
CH, S ~--N--N
~ ~
Claims (13)
1. An electrochromic system comprising at least one oxidizable substance RED1 which, by releasing electrons at an anode, is converted from a weakly colored or colorless form into a colored form OX1, and at least one reducible substance OX2 which, by accepting electrons at a cathode, is converted from a weakly colored or colorless form into a colored form RED2, the absorbance in the visible region of the spectrum increasing in each of these cases, and the weakly colored or colorless form being recovered in each case after charge equalization, wherein the reciprocal conversion of oxidized: and reducible form takes place by a .sigma. bond being broken or formed, respectively, for at least one of the comprised substances RED1 or OX2.
2. The electrochromic system as claimed in claim 1, which comprises, as the reducible substance OX2, a cyclic organic compound which, after accepting 1 or 2 electrons, is converted, one of the c bonds of the ring being broken, into an open-ring compound and which, by releasing 1 or 2 electrons, is converted once more into the cyclic starting compound, in each case precisely two electrons being transferred overall.
3. The electrochromic system as claimed in claims 1 and 2, which comprises, as the reducible substance OX2 which is converted reversibly, a .sigma. bond being broken, into the corresponding substance RED2, a compound selected from the group consisting of the tetrazolium salts, benzotriazolium salts, naphthotriazolium salts, cyclopropanes and [1.1.0]bicyclobutanes.
4. The electrochromic system as claimed in claims 1 to 3, which comprises, as the reducible substance OX2, at least one compound of the formulae , , , in which R1 to R5, independently of one another, represent C6- to C10-aryl or an aromatic or quasi-aromatic five- or six-membered heterocyclic ring, each of which is optionally benzanellated, R7, R9, R13 and R14, independently of one another, represent a radical of the formulae (V) to (VII) , , R8, R15 and R16, independently of one another, represent C6- to C10-aryl, C7-C11-aroyl or a radical of the formulae (V) to (VII), R10 to R12, R17 and R18, independently of one another, represent hydrogen, C1- to C4-alkyl, halogen or cyano, E1 and E2, independently of one another, represent O, S or N-R19, R19 and R22, independently of one another, represent C1- to C18-alkyl, C2- to C8-alkenyl, C4- to C7-cycloalkyl, C7- to C15-aralkyl or C6- to C10-aryl, R6, R20, R21, R23 and R24, independently of one another, represent hydrogen, C1- to C4-alkyl, C1- to C4-alkoxy, halogen, cyano, nitro or C1- to C4-alkoxycarbonyl, or R20 and R21, or R23 and R24, jointly form a -CH=CH-CH=CH- bridge, and X- represents a colorless anion which is redox-inert under the conditions.
5. The electrochromic system as claimed in claims 1 to 4, which comprises, as the oxidizable substance RED1, an organic compound which is able to release 2 electrons reversibly in two stages, the difference of the two oxidation statesbeing preferably at least 250 mV.
6. The electrochromic system as claimed in claims 1 to 5, which comprises, as the substance RED1 which is reversibly oxidizable in two stages, a compound of the formulae (VIII) to (XVII) , , , , , , , , , , in which R25 to R28, R31, R32, R35, R36, R43, R50 and R51, independently of one another, represent C1- to C18-alkyl, C2- to C12-alkenyl, C4- to C7-cycloalkyl, C7-to C15-aralkyl or C6- to C10-aryl, and R43, R50 and R51 additionally represent hydrogen, R29, R30, R33, R34, R37, R38, R39, to R42, R44, R45, R46 to R49 and R52 to R55, independently of one another, represent hydrogen, C1- to C4-alkyl, C1- to C4-alkoxy, halogen, cyano, nitro, C1- to C4-alkoxycarbonyl or C6- to C10-aryl, and R54 and R55 additionally represent an aromatic or quasi-aromatic five- or six-membered heterocyclic ring, each of which is optionally benzanellated, or a radical of the formulae (V) or (VI), and R45 additionally represents NR73R74, or R46 and R47 and/or R48 and R49 form a -(CH2)3-, -(CH2)4-, -(CH2)5- or -CH=CH-CH-CH- bridge, Z1 represents a direct bond, a -CH=CH- or -N=N- bridge, =Z2= represents a direct double bond, a =CH-CH= or =N-N= bridge, E3 to E5, E10 and E11, independently of one another, represent O, S, NR56 or C(CH3)2, and E5 additionally represents C=O or SO2, or E3 and E4, independently of one another, additionally represent -CH=CH-, E6 to E9, independently of one another, represent S, Se or NR56, R56, R73 and R74, independently of one another, represent C1- to C12-alkyl, C2- to C8-alkenyl, C4- to C7-cycloalkyl, C7- to C15-aralkyl or C6- to C10-aryl, and R73 additionally represents hydrogen, or R73 and R74, in the context of NR73R74, jointly with the N atom to which they are bound form a five- or six-membered saturated ring which may contain further heteroatoms, R65 to R72, independently of one another, represent hydrogen, C1- to C6-alkyl, C1- to C4-alkoxy, cyano, C1- to C4-alkoxycarbonyl or C6- to C10-aryl, and R65 and R66, and R71 and R72, independently of one another, may additionally form a -(CH2)3-, -(CH2)4- or -CH=CH-CH=CH- bridge, and u represents an integer between 0 and 10.
7. The electrochromic system as claimed in claim 1, which comprises at least one couple of oxidizable and reducible substances RED1/OX2.
8. The electrochromic system as claimed in claims 1 to 7, which comprises a couple RED1/OX2, the substance OX2 being a tetrazolinium salt of formula (I) as claimed in claim 4 in which R1 and R2 correspond to a radical of formula (XIX), and R3 corresponds to a radical of formula (XX), in which R57, R59 and R60, independently of one another, represent hydrogen, methyl, ethyl, methoxy, ethoxy, cyano, nitro, -N+(CH3)3 or COOH, or R57 and R59 jointly form an -O-CH2-O- bridge, R58 represents hydrogen, methyl, methoxy or chlorine, R61 represents methyl, difluoromethyl, trifluoromethyl, methoxycarbonyl, ethoxycarbonyl or phenyl, R62 represents hydrogen, methyl, ethyl, phenyl or chlorine, or R61 and R62 together form a -CH=CH-CH=CH- or -CH=CH-C(OCH3)=CH-bridge, E12 represents S, X- represents a colorless anion which is redox-inert under the conditions, and the substance RED1 being a compound selected from the group consisting of the formulae (VIII), (X), (XI), (XIV) and (XV) as claimed in claim 6, in which R25 to R28, R31, R32, R35, R36, R43 and R56 represent methyl, ethyl, propyl, butyl, pentyl, hexyl or benzyl, R25 to R28, R31 and R32, and R35 and R36, respectively, being identical and R43 additionally representing hydrogen, R29 and R44 represent hydrogen, R45 represents hydrogen, methoxy, ethoxy, dimethylamino, diethylamino, anilino, N-methylanilino or piperidino, R33 and R34 are identical and represent hydrogen, methyl, methoxy, chlorine, cyano of methoxycarbonyl, E3 to E5 represent O, S or NR56, but E3 and E4 are identical, R37 and R38 are identical and represent hydrogen, methyl, ethyl, propyl, butyl or phenyl, Z1 represents a direct bond or -CH=CH-, R46 to R49 are identical and represent hydrogen, methyl, methoxy, chlorine, cyano, methoxycarbonyl, ethoxycarbonyl or phenyl, E6 to E9 are identical and represent S, Se or NR56, =Z2= represents a direct double bond, a =CH-CH= or =N-N= bridge, R65 and R66, and R71 and R72 represent a -(CH2)3- or -(CH2)4- bridge, R67 to R70 represent hydrogen, and u represents an integer from 1 to 6.
9. The electrochromic system as claimed in claims 1 to 8, which comprises a couple of oxidizable and reducible substances RED1/OX2, RED1 and OX2 being linked via a bridge B and OX2 corresponding to a compound of the formulae (I) to (IV) as claimed in claim 4 and RED1 corresponding to one of the formulae (VIII) to (XVIII) as claimed in claim 6, in which B represents a bridge of the formulae -(CH2)n- or -[Y1s-(CH2)m-Y2]o-(CH2)p-Y3q-, which may be substituted by C1- to C4-alkyl, C1- to C4-alkoxy, halogen or phenyl, Y1 to Y3, independently of one another, represent O, S, NR63, COO, CONH, NHCONH, cyclopentanediyl; cyclohexanediyl, phenylene or naphthylene, R63 represents C1- to C6-alkyl, C2- to C6-alkenyl, C4- to C7-cycloalkyl, C7- to C15-aralkyl or C6- to C10-aryl, n represents an integer from 1 to 12, m and p, independently of one another, represent an integer from 0 to 8, o represents an integer from 0 to 6, q and s, independently of one another, represent 0 or 1, R19, R21, to R25, R31, R35, R39, R41, R43, R46, R50, R54, R56, R57, R59, R61, R62, R64, R65 or R66 form a direct bond to the bridge B, or R46, R57 or R59 form a -COO- bridge to the bridge B.
10. An electrochromic fluid comprising an electrochromic system as claimed in one of claims 1 to 9 and at least one inert solvent.
11. An electrochromic device containing an electrochromic fluid as claimed in claim 10.
12. The electrochromic device as claimed in claim 11, which is designed as a cell such as e.g. a solar cell, as a window pane, mirror, canopy or display.
13. The electrochromic device as claimed in claims 11 and 12, which comprises two transparent glass or plastic panes which face one another, one of which optionally being mirrored and whose sides which face one another are coated electroconductively, between which the electrochromic fluid is contained.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19605448A DE19605448A1 (en) | 1996-02-15 | 1996-02-15 | Electrochromic system |
| DE19605448.6 | 1996-02-15 | ||
| PCT/EP1997/000499 WO1997030135A1 (en) | 1996-02-15 | 1997-02-04 | Electrochromic system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2246478A1 true CA2246478A1 (en) | 1997-08-21 |
Family
ID=29421550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002246478A Abandoned CA2246478A1 (en) | 1996-02-15 | 1997-02-04 | Electrochromic system |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2246478A1 (en) |
-
1997
- 1997-02-04 CA CA002246478A patent/CA2246478A1/en not_active Abandoned
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