CN117700457A - Electrochromic compound, preparation method and application - Google Patents
Electrochromic compound, preparation method and application Download PDFInfo
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- CN117700457A CN117700457A CN202211084219.5A CN202211084219A CN117700457A CN 117700457 A CN117700457 A CN 117700457A CN 202211084219 A CN202211084219 A CN 202211084219A CN 117700457 A CN117700457 A CN 117700457A
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- Prior art keywords
- electrochromic
- compound
- drying
- product
- benzene
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 13
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229930192474 thiophene Natural products 0.000 claims abstract description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 54
- -1 triflate anions Chemical class 0.000 claims description 26
- 238000010992 reflux Methods 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 16
- 239000004065 semiconductor Substances 0.000 claims description 13
- 125000000304 alkynyl group Chemical group 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- IRTLROCMFSDSNF-UHFFFAOYSA-N 2-phenyl-1h-pyrrole Chemical group C1=CNC(C=2C=CC=CC=2)=C1 IRTLROCMFSDSNF-UHFFFAOYSA-N 0.000 claims description 5
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical group S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 claims description 5
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical group O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- BDEOXDSSZJCZPE-UHFFFAOYSA-N [1,3]thiazolo[4,5-d][1,3]thiazole Chemical group N1=CSC2=C1N=CS2 BDEOXDSSZJCZPE-UHFFFAOYSA-N 0.000 claims description 4
- ZEVVDSRCWJRHSX-UHFFFAOYSA-N 1,4-dibromo-2,5-bis(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC(Br)=C(C(F)(F)F)C=C1Br ZEVVDSRCWJRHSX-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- PDCBZHHORLHNCZ-UHFFFAOYSA-N 1,4-bis(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=C(C(F)(F)F)C=C1 PDCBZHHORLHNCZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000004984 smart glass Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 49
- 239000000203 mixture Substances 0.000 abstract description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 9
- 238000004873 anchoring Methods 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 5
- 230000021615 conjugation Effects 0.000 abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 189
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 72
- 238000001035 drying Methods 0.000 description 72
- 239000000047 product Substances 0.000 description 64
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 58
- 238000006243 chemical reaction Methods 0.000 description 49
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 36
- 239000000126 substance Substances 0.000 description 33
- 239000010410 layer Substances 0.000 description 31
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 24
- 239000012467 final product Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000012065 filter cake Substances 0.000 description 16
- 238000001914 filtration Methods 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 15
- UIWJXEAMDJCNOV-UHFFFAOYSA-N 1-chloro-3-(chloromethyl)-2,4,5,6-tetrafluorobenzene Chemical compound FC1=C(F)C(Cl)=C(F)C(CCl)=C1F UIWJXEAMDJCNOV-UHFFFAOYSA-N 0.000 description 14
- 238000000605 extraction Methods 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 14
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 12
- 239000012046 mixed solvent Substances 0.000 description 12
- HZAXFHJVJLSVMW-UHFFFAOYSA-N monoethanolamine hydrochloride Natural products NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 239000012044 organic layer Substances 0.000 description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- NNQDMQVWOWCVEM-UHFFFAOYSA-N 1-bromoprop-1-ene Chemical compound CC=CBr NNQDMQVWOWCVEM-UHFFFAOYSA-N 0.000 description 11
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005562 fading Methods 0.000 description 8
- QLULGIRFKAWHOJ-UHFFFAOYSA-N pyridin-4-ylboronic acid Chemical compound OB(O)C1=CC=NC=C1 QLULGIRFKAWHOJ-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 3
- FZAJTLGUMCMWRP-UHFFFAOYSA-N 4-(5-pyridin-4-ylthieno[3,2-b]thiophen-2-yl)pyridine Chemical compound c1c(sc2cc(sc12)-c1ccncc1)-c1ccncc1 FZAJTLGUMCMWRP-UHFFFAOYSA-N 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 2
- KBVDUUXRXJTAJC-UHFFFAOYSA-N 2,5-dibromothiophene Chemical compound BrC1=CC=C(Br)S1 KBVDUUXRXJTAJC-UHFFFAOYSA-N 0.000 description 2
- KBXDZYVLDKNMQL-UHFFFAOYSA-N 2,5-dipyridin-4-yl-[1,3]thiazolo[5,4-d][1,3]thiazole Chemical compound C1=NC=CC(C=2SC=3N=C(SC=3N=2)C=2C=CN=CC=2)=C1 KBXDZYVLDKNMQL-UHFFFAOYSA-N 0.000 description 2
- MAWKLXRVKVOYLR-UHFFFAOYSA-N 4-(4-pyridin-4-ylphenyl)pyridine Chemical compound C1=NC=CC(C=2C=CC(=CC=2)C=2C=CN=CC=2)=C1 MAWKLXRVKVOYLR-UHFFFAOYSA-N 0.000 description 2
- VUCGYYKDNQHHPD-UHFFFAOYSA-N 4-(5-pyridin-4-ylfuran-2-yl)pyridine Chemical compound C=1C=C(C=2C=CN=CC=2)OC=1C1=CC=NC=C1 VUCGYYKDNQHHPD-UHFFFAOYSA-N 0.000 description 2
- YLQPWBWBAUMDEE-UHFFFAOYSA-N 4-(5-pyridin-4-ylthiophen-2-yl)pyridine Chemical compound C=1C=C(C=2C=CN=CC=2)SC=1C1=CC=NC=C1 YLQPWBWBAUMDEE-UHFFFAOYSA-N 0.000 description 2
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229960003351 prussian blue Drugs 0.000 description 2
- 239000013225 prussian blue Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- CHCLRVOURKGRSW-UHFFFAOYSA-N 1,4-dibromo-2,5-dimethoxybenzene Chemical compound COC1=CC(Br)=C(OC)C=C1Br CHCLRVOURKGRSW-UHFFFAOYSA-N 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- WREHQSVHTIKEBB-UHFFFAOYSA-N 2,5-dibromo-1-phenylpyrrole Chemical compound BrC1=CC=C(Br)N1C1=CC=CC=C1 WREHQSVHTIKEBB-UHFFFAOYSA-N 0.000 description 1
- DMQSXYUWAHVIJY-UHFFFAOYSA-N 2,5-dibromo-3,4-bis(trifluoromethyl)thiophene Chemical compound BrC=1SC(=C(C1C(F)(F)F)C(F)(F)F)Br DMQSXYUWAHVIJY-UHFFFAOYSA-N 0.000 description 1
- MSUPZGGVRIRXAI-UHFFFAOYSA-N 2,5-dibromo-[1,3]thiazolo[5,4-d][1,3]thiazole Chemical compound S1C(Br)=NC2=C1N=C(Br)S2 MSUPZGGVRIRXAI-UHFFFAOYSA-N 0.000 description 1
- LACYYWKMIJOHLU-UHFFFAOYSA-N 2,5-dibromofuran Chemical compound BrC1=CC=C(Br)O1 LACYYWKMIJOHLU-UHFFFAOYSA-N 0.000 description 1
- APDAUBNBDJUQGW-UHFFFAOYSA-N 2,5-dibromothieno[3,2-b]thiophene Chemical compound S1C(Br)=CC2=C1C=C(Br)S2 APDAUBNBDJUQGW-UHFFFAOYSA-N 0.000 description 1
- GLISZRPOUBOZDL-UHFFFAOYSA-N 3-bromopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCBr GLISZRPOUBOZDL-UHFFFAOYSA-N 0.000 description 1
- FHMRWRBNAIDRAP-UHFFFAOYSA-N 5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=C(Br)SC(Br)=C21 FHMRWRBNAIDRAP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002146 bilateral effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XBPOBCXHALHJFP-UHFFFAOYSA-N ethyl 4-bromobutanoate Chemical compound CCOC(=O)CCCBr XBPOBCXHALHJFP-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
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- 238000006460 hydrolysis reaction Methods 0.000 description 1
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- 230000002427 irreversible effect Effects 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000005839 radical cations Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention relates to the technical field of electrochromic materials, and provides an electrochromic compound, which takes tetrabipyridine as a basic framework, benzene rings, thiophene, pyrrole, furan and derivatives thereof can be introduced into pyridine, and the electrochemical properties of the material can be regulated and controlled by expanding a conjugated structure; in addition, an asymmetric structure containing an anchoring group is designed, the anchoring group can modify the nano electrode, and the color-changing material is fixed at the electrode end, so that the color-changing speed is not affected by the diffusion structure of the material, and meanwhile, an unsaturated hydrocarbon structure is introduced at the other side, so that the solubility of the material can be improved, and the conjugation degree of the material is further increased. The compound is used as electrochromic material and has the advantages of rich color, fast color changing speed, long service life and the like. The device based on the material composition has the advantages of rich color change, high contrast ratio, high response speed, long service life of the device and the like.
Description
Technical Field
The invention relates to the technical field of electrochromic materials, in particular to an electrochromic compound and a preparation method thereof, an electrochromic device and a preparation method and application thereof.
Background
Electrochromic material is a material which can be reversibly changed in optical absorption under the action of an applied potential, and has great prospect in applications such as displays, intelligent windows, optical camouflage and the like. The inorganic electrochromic materials and the organic electrochromic materials can be classified by material essence classification. Common inorganic electrochromic materials are tungsten trioxide (WO 3 ) The organic electrochromic material such as Prussian Blue (PB) contains viologen (MV) 2+ ) Conjugated polymers (PEDOT, P3 HT), etc. Unlike thermochromic or photochromic devices, electrochromic exhibits better user control and color adjustment capabilities, making this technology a popular research topic.
Wherein the viologen is in a faded state (MV 2+ ) And coloring state (MV) +· ) The contrast ratio and the low driving voltage are very excellent, and are widely used in rearview mirrors of vehicles.
However, the current viologen color change materials are to be improved for two main reasons. The first is that the stability of small molecule viologen devices is poor, and due to the strong ion-pi interactions, the viologen radical cations dimerize, resulting in an irreversible fade process. Secondly, the color switching speed is too slow, because the fading speed of the viologen is influenced by the diffusion speed, most of the viologen has larger viscosity and molecular weight, thus leading to slow response speed and being unsuitable for practical application.
Disclosure of Invention
The current commercial electrochromic material mainly comprises viologen compounds, and has slower response speed and low stability. Meanwhile, although the material is already applied to the automobile rearview mirror, for outdoor application scenes, the material is required to meet the color selectivity and high sensitivity of users, so that the material has higher requirements on the fading speed and the stability of devices, and the current electrochromic material cannot meet the requirements of an outdoor intelligent window on the performance of the electrochromic material.
Aiming at the defects, the invention provides an electrochromic compound, a preparation method and application, and a device based on the electrochromic compound has important significance for application scenes needing rich colors and quick response.
The technical scheme of the invention is realized by the following steps: an electrochromic compound is provided, which has the following structural formula:
wherein R is 1 Is a phosphate group (-PO (OH) 2 ) Silicic acid group (-Si (OH)) 3 ) And one of an acetate group (-COOH);
m is a direct bond, or M is selected from benzene, 1, 4-dibromo-2, 5-bis (trifluoromethyl) benzene, thiophene, furan, phenylpyrrole, thienothiophene, 2, 3-dihydrothieno [3,4-b ] [1,4] dioxin, thiazolothiazole and substituted derivatives thereof;
R 2 alkenyl or alkynyl;
m and n may be each independently an integer of 0 to 12;
X - selected from chloride, bromide, iodide, triflate anions, perchlorate anions, tetrafluoroborate anions.
Preferably, in one embodiment of the present invention, the electrochromic compound has the structures of the following formulas (a) to (F):
preferably, in one embodiment of the inventionIn embodiments, R of electrochromic compounds 2 Is an unsaturated alkenyl or alkynyl group; the alkenyl group includes a vinyl group (-ch=ch) 2 ) Allyl (-CH) 2 CH＝CH 2 ) The method comprises the steps of carrying out a first treatment on the surface of the The alkynyl group includes an ethynyl group (-C≡CH), a propargyl group (-CH) 2 C.ident.CH), 1-propynyl (-C.ident.C-CH) 3 )。
Preferably, in one embodiment of the present invention, the electrochromic compound has any one of the structural formulas shown in formulas (1) to (9):
the invention also provides a preparation method of the electrochromic compound, which comprises the following steps:
reacting and refluxing the compound a with the compound b to obtain a compound c, refluxing the compound c and the compound d in an organic solvent to obtain a compound e, and finally acidifying and hydrolyzing to obtain the final electrochromic compound;
wherein M is a direct bond, or M is selected from benzene, 2, 5-bis (trifluoromethyl) benzene, thiophene, furan, phenylpyrrole, thienothiophene, 2, 3-dihydrothieno [3,4-b ] [1,4] dioxin, thiazolothiazole and substituted derivatives thereof;
the structural formula of the compound b is R 3 -(CH2) m -R 4 M is an integer between 0 and 12, R 3 Is any one of I, br and Cl, R 4 Is a substituted phosphate (-PO (OCH) 2 CH 3 ) 2 ) Methylsiloxane (-Si (OCH) 3 ) 3 ) Ethyl acetate (-COOCH) 2 CH 3 ) One of the following;
the structural formula of the compound d is R 2 -(CH2) n -R 5 N is an integer of 0 to 12, R 2 Is alkenyl or alkynyl, R 5 Is any one of I, br and Cl.
Preferably, in one embodiment of the invention, m is 2 or 3 and n is 2 or 3.
Preferably, in one embodiment of the present invention, the structural formula of the compound b is one of the following:
the structural formula of the compound d is one of the following:
preferably, in one embodiment of the invention, the M is at the 2 and/or 5 position from F, CF 3 、OCH 3 、OCF 3 Any one of substituted benzene;
or M is pyrrole substituted by benzene, benzyl and derivatives thereof at the N position;
alternatively, M is 2 and/or the 3 position is defined by CF 3 、OCH 3 、OCF 3 Pyrrole or thiophene of any kind.
The invention also provides an electrochromic device comprising a first conductive layer, a second conductive layer, a semiconductor layer, an electrochromic layer, and an electrolyte layer between the first conductive layer and the second conductive layer; the electrochromic layer uses the electrochromic compound or the electrochromic compound obtained by the preparation method.
Preferably, in one embodiment of the present invention, the first conductive layer and the second conductive layer comprise one of FTO, ITO conductive glass; the semiconductor layer comprises one of titanium dioxide and tin dioxide;
preferably, in one embodiment of the present invention, the semiconductor layer is titanium dioxide;
preferably, in one embodiment of the present invention, the first conductive layer and the second conductive layer are FTOs.
Preferably, in one embodiment of the present invention, the concentration of the material in the electrochromic layer may be 5mg/mL,10mg/mL,15mg/mL,20mg/mL,30mg/mL;
preferably, in one embodiment of the present invention, the electrochromic layer has a material concentration of 10mg/mL;
preferably, in one embodiment of the present invention, the electrolyte layer includes an electrolyte and a solvent. The electrolyte comprises one or more of lithium perchlorate, lithium chloride and lithium bistrifluoromethane sulfonyl imide; the solvent comprises propylene carbonate, tetrahydrofuran, acetonitrile, N-dimethylformamide, dimethyl sulfoxide, toluene, xylene, ethyl acetate and other high boiling point solvents;
preferably, in one embodiment of the present invention, the electrolyte is lithium chloride;
preferably, in one embodiment of the present invention, the solvent is propylene carbonate;
preferably, in one embodiment of the invention, the concentration of the electrolyte is 0.1M.
Preferably, in one embodiment of the present invention, the preparation process includes: the electrochromic material solution was immersed in the semiconductor layer for grafting for 24 hours, and the electrolyte layer was filled between the semiconductor layer and the second conductive layer.
Preferably, in one embodiment of the present invention, the preparation process includes: coating a semiconductor layer on the first conductive layer, and grafting an electrochromic layer on the semiconductor layer;
preferably, in one embodiment of the present invention, the preparation process includes: the electrochromic device includes a semiconductor layer and a second conductive layer defining a fill space therebetween, the method comprising: and filling the electrolyte layer into the filling space, and sealing to obtain the electrochromic device.
The invention also provides an electrochromic device, and application of the electrochromic device in intelligent windows, rearview mirrors or electronic equipment.
The beneficial effects are as follows:
the electrochromic compound provided by the invention takes tetrabipyridine as a basic framework, benzene ring, thiophene, pyrrole, furan and derivatives thereof can be introduced into pyridine, and the electrochemical property of the material can be regulated and controlled by expanding a conjugated structure; in addition, an asymmetric structure containing an anchoring group is designed, the anchoring group can modify the nano electrode, and the color-changing material is fixed at the electrode end, so that the color-changing speed is not affected by the diffusion structure of the material, and meanwhile, an unsaturated hydrocarbon structure is introduced at the other side, so that the solubility of the material can be improved, and the conjugation degree of the material is further increased. The compound is used as electrochromic material and has the advantages of rich color, fast color changing speed, long service life and the like. The device based on the material composition has the advantages of rich color change, high contrast ratio, high response speed, long service life of the device and the like.
Drawings
FIG. 1 shows a schematic structural diagram of an electrochromic device according to one example of the present application;
FIG. 2 shows a cyclic voltammogram of one of the devices;
fig. 3 shows the optical stability diagram at 600nm of the electrochromic device of one of the devices, the voltage for color switching being-1.5 v,5s, +1.5v,5s, 1000 cycles.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments of the present invention and corresponding drawings. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention will now be described in further detail with reference to the drawings and examples.
The synthesis of the target compound comprises four steps:
the first step is to synthesize compound a by reaction with 4-pyridineboronic acid containing either a dibromo or a chloro-substituted M. Wherein M can be a direct bond or benzene ring, thiophene, pyrrole, thienothiophene, thiazole and substituted derivatives thereof,
the reaction equation is as follows:
the second step is to synthesize a viologen compound with an anchoring group on one side, and to react the compound a with at least one of halogenated phosphate, carboxylate and methylsiloxane. Wherein R is 4 Is a substituted phosphate (-PO (OCH) 2 CH 3 ) 2 ) Methylsiloxane (-Si (OCH) 3 ) 3 ) Ethyl acetate (-COOCH) 2 CH 3 ) One of the following; the reaction equation is as follows:
the third step is to obtain a bilateral substituted pyridine derivative, wherein R 2 For unsaturated alkenyl or alkynyl, alkenyl includes vinyl (-ch=ch) 2 ) Allyl (-CH) 2 CH＝CH 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Alkynyl groups include ethynyl (-C.ident.CH), propargyl (-CH) 2 C.ident.CH), 1-propynyl (-C.ident.C-CH) 3 ) The reaction equation is as follows:
the fourth step is hydrolysis in an acidic environment, wherein R 1 Is a substituted phosphoric acid (-PO (OH) 2 ) Silicic acid (-Si (OH)) 3 ) And one of carboxylic acids (-COOH), the reaction equation is as follows:
example 1
2mol of 4-4' -bipyridine were placed in a pear-shaped bottle, followed by 50mL of Acetonitrile (ACN), followed by slow addition of 1mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After the reaction is completed, ethyl acetate is used for precipitation, and the monosubstituted viologen derivative is obtained. The resulting first step product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a second-step product. Finally, the second step of product is placed in a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(400MHz,DMSO)δ9.08(dd,4H),8.96(dd,4H),5.29(d,2H),5.08(d,2H),4.80(s,2H),2.42(d,2H),1.55-1.48(m,5H)ppm.
example 2
1mol of 2, 5-dibromothiophene, 3mol of 4-pyridineboronic acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into a reaction bottle under a nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1h, distilling under reduced pressure, and purifying by silica gel column to obtain the 2, 5-di (pyridine-4-yl) thiophene. Next, 1mol of 2, 5-di (pyridin-4-yl) thiophene was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying the acetonitrile to obtain the product,dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ for 12 hours in a vacuum drying oven to obtain the product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.91,8.78,7.79,7.60,7.40,6.00,5.93,5.25,5.22,5.21,5.19,4.95,4.93,4.86,4.83,4.63,3.39,3.36,3.31,3.28.
example 3
1mol of 2, 5-dibromo-3, 4-bis (trifluoromethyl) thiophene, 3mol of 4-pyridineboronic acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into a reaction bottle under a nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1h, distilling under reduced pressure, and purifying by silica gel column to obtain the product 4,4' - (3, 4-bis (trifluoromethyl) thiophene-2, 5-diyl) bipyridine in the first step. Next, 1mol of 4,4' - (3, 4-bis (trifluoromethyl) thiophene-2, 5-diyl) bipyridine was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to the pear-shaped flask in equimolar ratio to propargyl bromide, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added,reflux was carried out at 100℃for 10h. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.81(s,2H),8.76(s,2H),7.80(s,2H),7.65(s,2H),5.93(s,2H),4.67(s,2H),4.63(s,2H),3.27(s,2H),2.94(s,2H),2.64(s,1H).
example 4
1mol of 2, 5-dibromo-thieno [3,2-b]Thiophene, 3mol of 4-pyridine boric acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into a reaction bottle under the nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1h, distilling under reduced pressure, and purifying with silica gel column to obtain the final product 2, 5-di (pyridin-4-yl) thieno [3,2-b ]]Thiophene. Next 1mol of 2, 5-di (pyridin-4-yl) thieno [3,2-b]Thiophene, 50mL of Acetonitrile (ACN) was poured, followed by slow addition of 0.5mol of (3-bromopropyl) trimethoxysilane. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second step product was then reacted with bromopolyl (Br-CH) 2 C≡ch) was added to the pear-shaped flask in equimolar ratio, and 50mL ACN was added thereto and stirred for 24 hours. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows:
1 H NMR(500MHz,Chloroform-d)δ8.82(s,5H),7.73(s,2H),7.56(s,3H),7.49(s,2H),6.41(s,3H),5.04(d,J＝12.5Hz,1H),4.86(d,J＝12.5Hz,1H),4.43(s,2H),2.89(s,1H),2.13–2.06(m,4H),2.01(d,J＝12.3Hz,1H).
example 5
1mol of 1, 4-dibromobenzene, 3mol of 4-pyridineboronic acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into a reaction bottle under a nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the filter residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined, poured into an erlenmeyer flask containing anhydrous Na2SO4, dried for 1h, distilled under reduced pressure, and finally purified by a silica gel column to give the first step of product 1, 4-di (pyridin-4-yl) benzene. Next, 1mol of 1, 4-di (pyridin-4-yl) benzene was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of ethyl 4-bromobutyrate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
Of chemical structureThe characterization is as follows: 1 H NMR(500MHz,Chloroform-d)δ9.01(s,2H),8.56(s,2H),7.74(d,J＝7.5Hz,4H),7.66(s,4H),6.00(s,1H),5.22(s,2H),4.94(d,J＝12.5Hz,1H),4.84(d,J＝12.5Hz,1H),4.65(s,2H),2.50(d,J＝12.5Hz,1H),2.44(d,J＝12.5Hz,1H),2.26(s,2H).
example 6
1mol of 1, 4-dibromo-2, 5-bis (trifluoromethyl) benzene, 3mol of 4-pyridineboronic acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into a reaction bottle under a nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1h, distilling under reduced pressure, and purifying by silica gel column to obtain the product 4,4' - (2, 5-bis (trifluoromethyl) -1, 4-phenylene) bipyridine in the first step. Next, 1mol of 4,4' - (2, 5-bis (trifluoromethyl) -1, 4-phenylene) bipyridine was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.81(s,2H),8.76(s,2H),7.78(s,2H),7.65(d,J＝3.1Hz,4H),5.99(s,1H),5.93(s,2H),5.19(s,2H),4.94(d,J＝12.5Hz,1H),4.79(d,J＝12.5Hz,1H),4.63(s,2H),3.27(s,2H).
example 7
1mol of 1, 4-dibromo-2, 5-dimethoxybenzene, 3mol of 4-pyridineboronic acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into the reaction flask under a nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1h, distilling under reduced pressure, and purifying by silica gel column to obtain the product 4,4' - (2, 5-dimethoxy-1, 4-phenylene) bipyridine in the first step. Next, 1mol of 4,4' - (2, 5-dimethoxy-1, 4-phenylene) bipyridine was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.78(d,J＝15.0Hz,5H),7.75(s,3H),7.62(s,3H),7.04(s,2H),6.00(s,1H),5.20(s,2H),4.94(d,J＝12.5Hz,1H),4.79(d,J＝12.5Hz,1H),4.64(s,2H),3.87(s,6H),2.47(d,J＝12.4Hz,1H),2.41(d,J＝12.4Hz,1H),2.36(d,J＝12.3Hz,1H),2.26(d,J＝12.5Hz,1H).
example 8
1mol of 5, 7-dibromo-2, 3-dihydrothieno [3,4-b][1,4]Dioxin, 3mol of 4-pyridine boric acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into a reaction bottle under the nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1h, distilling under reduced pressure, and purifying with silica gel column to obtain the final product 5, 7-di (pyridin-4-yl) -2, 3-dihydrothieno [3,4-b ]][1,4]Dioxin. Next 1mol of 5, 7-bis (pyridin-4-yl) -2, 3-dihydrothieno [3,4-b][1,4]Dioxin, pour into 50mL of Acetonitrile (ACN), then slowly add 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.99(s,2H),8.87(s,2H),7.56(s,2H),7.51(s,2H),6.12(s,2H),6.00(s,1H),5.19(s,2H),4.94(d,J＝12.5Hz,1H),4.79(d,J＝12.5Hz,1H),4.63(s,2H),4.32(d,J＝8.8Hz,3H),4.27(s,1H),3.43(d,J＝12.5Hz,1H),3.32(d,J＝12.3Hz,1H).
example 9
1mol of 2, 5-dibromo-1-phenyl-1H-pyrrole, 3mol of 4-pyridine boric acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into the reaction flask under the nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1H, distilling under reduced pressure, and purifying by silica gel column to obtain the product 4,4' - (1-phenyl-1H-pyrrole-2, 5-diyl) bipyridine in the first step. Next, 1mol of 4,4' - (1-phenyl-1H-pyrrole-2, 5-diyl) bipyridine was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.87(s,2H),8.81(s,2H),7.94(s,2H),7.77(s,2H),7.54–7.34(m,8H),6.12(s,2H),6.00(s,1H),5.19(s,2H),4.87(d,J＝12.3Hz,1H),4.71(d,J＝12.4Hz,1H),4.63(s,2H),3.38(d,J＝12.3Hz,1H),3.27(d,J＝12.5Hz,1H).
example 10
1mol of 2, 5-dibromo-1- (4- (trifluoromethoxy) benzyl) -1H-pyrrole, 3mol of 4-pyridineboronic acid, 8mThe potassium carbonate of the ol is added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into a reaction bottle under the nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1H, distilling under reduced pressure, and purifying by silica gel column to obtain the product 4,4' - (1- (4- (trifluoromethoxy) benzyl) -1H-pyrrole-2, 5-diyl) bipyridine in the first step. Next, 1mol of 4,4' - (1- (4- (trifluoromethoxy) benzyl) -1H-pyrrole-2, 5-diyl) bipyridine was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product.
The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.82(s,2H),8.76(s,2H),7.77(d,J＝7.5Hz,4H),7.44(s,2H),7.27–7.18(m,5H),5.97(s,1H),5.93(s,2H),5.49(dt,J＝12.3,1.0Hz,1H),5.39(dt,J＝12.4,1.0Hz,1H),5.19(s,2H),4.94(d,J＝12.3Hz,1H),4.79(d,J＝12.5Hz,1H),4.64(s,2H),3.27(s,2H).
example 11
1mol of 2, 5-dibromofuran, 3mol of 4-pyridineboronic acid, 8mol of potassium carbonate are added to the dryThen injecting a mixed solvent of 1, 4-dioxane, ethanol and triethylamine into a reaction bottle under the nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1h, distilling under reduced pressure, and purifying by silica gel column to obtain the 2, 5-di (pyridin-4-yl) furan as the first step product. Next, 1mol of 2, 5-di (pyridin-4-yl) furan was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ9.12(s,1H),9.00(s,1H),7.87(s,2H),7.16(s,1H),6.00(s,0H),5.93(s,1H),5.22(s,1H),4.95(s,1H),4.63(s,1H),3.46–3.34(m,1H).
example 12
1mol of 2, 5-dibromothiazolo [5,4-d ] thiazole, 3mol of 4-pyridine boric acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into the reaction flask under the nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10% (mol) of Pd (PPh 3) 4 was poured rapidly into a bottle and stirred at 100℃for 24h. After cooling to room temperature, the filter residue is washed with DCM, the filtrate is separated and extracted, the organic layers are combined, poured into an conical flask filled with anhydrous Na2SO4, dried for 1h, distilled under reduced pressure, and finally purified by a silica gel column to obtain the product of the first step, namely 2, 5-di (pyridine-4-yl) thiazolo [5,4-d ] thiazole. Next, 1mol of 2, 5-di (pyridin-4-yl) thiazolo [5,4-d ] thiazole was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ9.01(s,2H),8.85(s,2H),8.12(s,2H),8.01(s,2H),6.12(s,2H),6.00(s,1H),5.19(s,2H),4.94(d,J＝12.5Hz,1H),4.79(d,J＝12.5Hz,1H),4.63(s,2H),3.43(d,J＝12.5Hz,1H),3.32(d,J＝12.3Hz,1H).
example 13
1mol of 2, 5-dibromothiophene [3,2-b ] thiophene, 3mol of 4-pyridine boric acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into the reaction flask under the nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10% (mol) of Pd (PPh 3) 4 was poured rapidly into a bottle and stirred at 100℃for 24h. After cooling to room temperature, the filter residue is washed with DCM, the filtrate is separated and extracted, the organic layers are combined, poured into an conical flask filled with anhydrous Na2SO4, dried for 1h, distilled under reduced pressure, and finally purified by a silica gel column to obtain the product of the first step, namely 2, 5-di (pyridine-4-yl) thieno [3,2-b ] thiophene. Next, 1mol of 2, 5-di (pyridin-4-yl) thieno [3,2-b ] thiophene was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1H NMR (500 MHz, chloroform-d) δ8.85 (s, 2H), 8.81 (s, 2H), 7.84 (s, 2H), 7.74 (s, 2H), 7.56 (s, 2H), 6.12 (s, 2H), 6.00 (s, 1H), 5.19 (s, 2H), 4.94 (d, J=12.5 Hz, 1H), 4.79 (d, J=12.5 Hz, 1H), 4.63 (s, 2H), 3.38 (d, J=12.3 Hz, 1H), 3.27 (d, J=12.5 Hz, 1H).
Comparative example 1
2mol of 4-4' -bipyridine were placed in a pear-shaped bottle, followed by 50mL of Acetonitrile (ACN), followed by slow addition of 1mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After the reaction is completed, ethyl acetate is used for precipitation, and the monosubstituted viologen derivative is obtained. The resulting first step product was then added to a pear-shaped flask in equimolar ratio to bromopropane, and 50mL ACN was added and stirred for 24 hours. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a second-step product. Finally, the second step of product is placed in a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.79(d,J＝7.8Hz,5H),7.92(s,2H),7.72(s,2H),6.04(s,2H),4.59(s,2H),4.34(s,2H),3.30(s,2H),1.97(s,2H),0.98(s,3H).
comparative example 2
2mol of 4-4' -bipyridine were placed in a pear-shaped bottle, followed by 50mL of Acetonitrile (ACN), followed by slow addition of 2mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After the reaction was completed, acetonitrile was dried by spin-drying, dissolved in water, extracted by adding methylene chloride, dried by spin-drying, and dried in a vacuum oven at 60℃for 12 hours. Finally, excess dilute hydrochloric acid was added and the mixture was refluxed at 100℃for 10 hours. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.76(s,1H),7.85(s,1H),5.93(s,1H),4.63(s,1H),3.37(s,1H).
comparative example 3
2mol of 4-4' -bipyridine were placed in a pear-shaped bottle, followed by 50mL of Acetonitrile (ACN), followed by slow addition of 2mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After the reaction was completed, acetonitrile was dried by spin-drying, dissolved in water, extracted by adding methylene chloride, dried by spin-drying, and dried in a vacuum oven at 60℃for 12 hours. Finally, excess dilute hydrochloric acid was added and the mixture was refluxed at 100℃for 10 hours. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows:
the chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.79(s,2H),7.89(s,2H),4.33(s,2H),1.97(s,2H),0.96(s,3H).
results examples
The cathode electrochromic materials synthesized in examples 1 to 13 and comparative examples 1 to 3 described above were applied to electrochromic devices, respectively. It should be noted that the electrochromic materials of the cathodes synthesized in examples 1 to 13 and comparative examples 1 to 3 are prepared by salifying chloride ions, and the electrochromic materials prepared by salifying bromide ions, iodide ions, triflate anions, perchlorate anions and tetrafluoroborate anions have similar properties to those of chloride ions, and are not described in detail herein.
The preparation method comprises the following steps of 2 The slurry was knife coated onto FTO, heated to 120 degrees celsius at a rate of 10 degrees per minute, held for 30 minutes and then annealed. TiO is mixed with 2 immersing/FTO in the solution of viologen with different concentrations for 12h, washing with deionized water and ethanol, and drying in a vacuum drying oven at 60 ℃. Adsorbed viologen/TiO 2 The FTO is closely attached to the other ITO with the 3M double faced adhesive tape around, and electrolyte is injected; preferably, the electrolyte is 0.1M LiClO 4 PC solution, tiO of (C) 2 The thickness is 3 μm. The electrochromic device is obtained after assembly, and the specific structure of the electrochromic device is shown in fig. 1.
After the device was assembled, we performed a series of studies on electrochromic devices based on the above examples, and tested the transmittance at the characteristic peak with time, thereby obtaining the coloring time (t coloring ) And fade time (t) bleaching ) The results are shown in Table 1.
TABLE 1
As seen from table 1, the difference in M structure affects the driving voltage of the device depending on the electronegativity of the M cell, and if the M electrons have electron withdrawing ability, the HOMO-LUMO energy level can be lowered, thereby lowering the driving voltage. As in examples 1,2 and 6, which are electron withdrawing units, the voltage to drive the device to change color is relatively low; in the embodiment 7, the methoxy group contained in the benzene ring belongs to an electron donating group, so that the driving voltage can be increased, and in the embodiment 9, the electron cloud distribution is more uniform due to the conjugation of the phenylpyrrole, so that the driving voltage is increased; second, the M group can affect the final color of the device, as in examples 8-10 for pink and example 1 for blue-violet; second, the coloring and fading time of the material is affected by the molecular weight of the material, steric hindrance, and the color switching speed is the slowest as in example 9.
The electrochromic device prepared by the invention has the characteristics of high contrast ratio and rapid color switching, and the cyclic voltammogram of the device is stable and the driving voltage required by color change is low as shown in the figure 2; as can be seen from fig. 3, the color switching speed of the device is about 1s, the contrast is close to 70%, the device can be continuously switched 10000 times, and no optical attenuation occurs.
To demonstrate the characteristics of this example, a comparative example was designed and synthesized. Comparative example 1 is an anchoring structure containing a butyl structure. From the test results, the color of the material is single, blue due to the absence of the incorporated M units, and the discoloration and fading speed of the device is slower than that of the examples due to the high steric hindrance of the alkyl groups; comparative example 2 is a viologen containing a double-sided anchoring group, the material color exhibiting a blue color due to the absence of incorporated M units. In addition, the device composed of the material has a very low color-changing and fading speed because the viologen with anchoring groups on both sides is tightly adsorbed on the semiconductor layer, so that the intercalation and deintercalation of ions are difficult, and the device has lower stability than the embodiment during the test because the electron cloud of the material is highly concentrated in bipyridylium salt; comparative example 3 is a structure without anchor groups and alkynyl groups, and the rate of discoloration and fading of the device is limited by diffusion of the material itself, since there is no chemisorption with the semiconductor, and thus the rate of discoloration and fading of the device is the slowest.
According to the electrochromic material prepared by the embodiment of the invention, unsaturated alkyne, especially allyl and propargyl, is introduced, free radical polymerization cannot be performed due to the structural characteristics of the electrochromic material, and meanwhile, the conjugated structure can be effectively further expanded, the electron cloud density is reduced, and the stability of the material is improved; secondly, the short and small alkyne structure has the characteristic of small steric hindrance. The other end of the color-changing material has low steric hindrance after being subjected to chemical adsorption with the semiconductor layer, so that the intercalation and deintercalation of ions can be promoted, and the color switching speed of the electrochromic device is improved. Furthermore, the presence of the unique anchoring structure chemisorbs to the semiconductor layer, so that discoloration and fading of the device is not limited by diffusion of the material itself. The above features enable us to obtain high performance electrochromic devices beyond those based on conventional material devices.
The primers listed above are only partially representative, and other electrochromic compounds containing the same ideas are within the scope of this patent.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. An electrochromic compound characterized by the following structural formula:
wherein R is 1 Is phosphate-PO (OH) 2 Silicic acid radical-Si (OH) 3 And one of acetate-COOH;
m is a direct bond, or M is selected from benzene, 1, 4-dibromo-2, 5-bis (trifluoromethyl) benzene, thiophene, furan, phenylpyrrole, thienothiophene, 2, 3-dihydrothieno [3,4-b ] [1,4] dioxin, thiazolothiazole and substituted derivatives thereof;
R 2 alkenyl or alkynyl;
m and n may be each independently an integer of 0 to 12;
X - selected from chloride, bromide, iodide, triflate anions, perchlorate anions, tetrafluoroborate anions.
2. Electrochromic compound according to claim 1, characterized in that it has the structure of formulae (a) to (F) as follows:
3. electrochromic compound according to claim 1, characterized in that R 2 Is an unsaturated alkenyl or alkynyl group; the alkenyl group includes vinyl-ch=ch 2 allyl-CH 2 CH＝CH 2 The method comprises the steps of carrying out a first treatment on the surface of the The alkynyl group includes ethynyl-C.ident.CH, propargyl-CH 2 C.ident.CH, 1-propynyl-C.ident.C-CH 3 。
4. The electrochromic compound according to claim 1, characterized by having any one of the structural formulae shown in formulae (1) to (9):
5. electrochromic compound according to claim 1, characterized in that M is in position 2 and/or 5 by F, CF 3 、OCH 3 、OCF 3 Any one of substituted benzene;
or M is pyrrole substituted by benzene, benzyl and derivatives thereof at the N position;
alternatively, M is 2 and/or the 3 position is defined by CF 3 、OCH 3 、OCF 3 Pyrrole or thiophene of any kind.
6. A method for producing an electrochromic compound according to any one of claims 1 to 5, characterized by comprising the steps of:
reacting and refluxing the compound a with the compound b to obtain a compound c, refluxing the compound c and the compound d in an organic solvent to obtain a compound e, and finally acidifying and hydrolyzing to obtain the final electrochromic compound;
wherein M is a direct bond, or M is selected from benzene, 2, 5-bis (trifluoromethyl) benzene, thiophene, furan, phenylpyrrole, thienothiophene, 2, 3-dihydrothieno [3,4-b ] [1,4] dioxin, thiazolothiazole and substituted derivatives thereof;
the structural formula of the compound b is R 3 -(CH2) m -R 4 M is an integer between 0 and 12, R 3 Is any one of I, br and Cl, R 4 Is a substituted phosphate (-PO (OCH) 2 CH 3 ) 2 ) Methylsiloxane (-Si (OCH) 3 ) 3 ) Ethyl acetate (-COOCH) 2 CH 3 ) One of the following;
the structural formula of the compound d is R 2 -(CH2) n -R 5 N is an integer of 0 to 12, R 2 Is alkenyl or alkynyl, R 5 Is any one of I, br and Cl.
7. The method of claim 6, wherein m is 2 or 3 and n is 2 or 3.
8. The method of claim 6, wherein the compound b has one of the following structural formulas:
the structural formula of the compound d is one of the following:
9. an electrochromic device comprising a first conductive layer, a second conductive layer, a semiconductor layer, an electrochromic layer, and an electrolyte layer between the first conductive layer and the second conductive layer; the electrochromic layer uses the electrochromic compound according to any one of claims 1 to 5 or the electrochromic compound obtained by the production method according to any one of claims 6 to 8.
10. Use of the electrochromic device of claim 9 in a smart window, a rearview mirror or an electronic device.
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