CN110003233A - 一类硫族元素桥联的紫罗精小分子、聚合物、衍生物及其应用 - Google Patents
一类硫族元素桥联的紫罗精小分子、聚合物、衍生物及其应用 Download PDFInfo
- Publication number
- CN110003233A CN110003233A CN201910270580.9A CN201910270580A CN110003233A CN 110003233 A CN110003233 A CN 110003233A CN 201910270580 A CN201910270580 A CN 201910270580A CN 110003233 A CN110003233 A CN 110003233A
- Authority
- CN
- China
- Prior art keywords
- chalcogen
- purple sieve
- sieve essence
- diquinoline
- purple
- 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.)
- Pending
Links
- 229910052798 chalcogen Inorganic materials 0.000 title claims abstract description 104
- 150000001787 chalcogens Chemical group 0.000 title claims abstract description 104
- 229920000642 polymer Polymers 0.000 title claims abstract description 49
- 150000003384 small molecules Chemical class 0.000 title claims abstract description 30
- 125000001979 organolithium group Chemical group 0.000 claims abstract description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 11
- 229910052714 tellurium Chemical group 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 229910052711 selenium Inorganic materials 0.000 claims description 16
- 239000011669 selenium Chemical group 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 229920000344 molecularly imprinted polymer Polymers 0.000 claims description 13
- -1 Methyl Chemical group 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000003292 glue Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 239000000853 adhesive Substances 0.000 claims description 9
- 230000001070 adhesive effect Effects 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 4
- 239000011889 copper foil Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 2
- 208000002925 dental caries Diseases 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims 2
- ZBPLCNNFMMPYQZ-UHFFFAOYSA-N C1(OCCO1)=O.P(=O)(O)(O)O Chemical compound C1(OCCO1)=O.P(=O)(O)(O)O ZBPLCNNFMMPYQZ-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 21
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- 229910052717 sulfur Inorganic materials 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000001376 precipitating effect Effects 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 238000003828 vacuum filtration Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 238000005349 anion exchange Methods 0.000 description 4
- 150000001503 aryl iodides Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 150000001786 chalcogen compounds Chemical class 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 229940125898 compound 5 Drugs 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 238000004847 absorption spectroscopy Methods 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- ZGIKWINFUGEQEO-UHFFFAOYSA-N 3-bromoquinoline Chemical compound C1=CC=CC2=CC(Br)=CN=C21 ZGIKWINFUGEQEO-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001347 alkyl bromides Chemical class 0.000 description 2
- 150000001351 alkyl iodides Chemical class 0.000 description 2
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001499 aryl bromides Chemical class 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- XJTQJERLRPWUGL-UHFFFAOYSA-N iodomethylbenzene Chemical compound ICC1=CC=CC=C1 XJTQJERLRPWUGL-UHFFFAOYSA-N 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical compound COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- QAPTWHXHEYAIKG-RCOXNQKVSA-N n-[(1r,2s,5r)-5-(tert-butylamino)-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](NC(C)(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 QAPTWHXHEYAIKG-RCOXNQKVSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BBNQQADTFFCFGB-UHFFFAOYSA-N purpurin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC(O)=C3C(=O)C2=C1 BBNQQADTFFCFGB-UHFFFAOYSA-N 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- SWLJJEFSPJCUBD-UHFFFAOYSA-N tellurium tetrachloride Chemical compound Cl[Te](Cl)(Cl)Cl SWLJJEFSPJCUBD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SHAHPWSYJFYMRX-GDLCADMTSA-N (2S)-2-(4-{[(1R,2S)-2-hydroxycyclopentyl]methyl}phenyl)propanoic acid Chemical compound C1=CC([C@@H](C(O)=O)C)=CC=C1C[C@@H]1[C@@H](O)CCC1 SHAHPWSYJFYMRX-GDLCADMTSA-N 0.000 description 1
- QKLXBIHSGMPUQS-FGZHOGPDSA-M (3r,5r)-7-[4-(4-fluorophenyl)-2,5-dimethyl-1-phenylpyrrol-3-yl]-3,5-dihydroxyheptanoate Chemical compound CC1=C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)C(C=2C=CC(F)=CC=2)=C(C)N1C1=CC=CC=C1 QKLXBIHSGMPUQS-FGZHOGPDSA-M 0.000 description 1
- OVDGUTHABMXVMI-UHFFFAOYSA-N 3-nitro-4-(propylamino)benzoic acid Chemical compound CCCNC1=CC=C(C(O)=O)C=C1[N+]([O-])=O OVDGUTHABMXVMI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- TZYWCYJVHRLUCT-VABKMULXSA-N N-benzyloxycarbonyl-L-leucyl-L-leucyl-L-leucinal Chemical compound CC(C)C[C@@H](C=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CC(C)C)NC(=O)OCC1=CC=CC=C1 TZYWCYJVHRLUCT-VABKMULXSA-N 0.000 description 1
- TZCCKCLHNUSAMQ-DUGSHLAESA-N NC(=O)C[C@H](NC(=O)[C@H](CCCNC(=N)N)NC(=O)[C@@H]1CCCN1C(=O)[C@H](CCCNC(=N)N)NC(=O)[C@H](Cc2ccc(F)cc2)NC(=O)[C@H](Cc3c[nH]c4ccccc34)NC(=O)Cc5cccs5)C(=O)N Chemical compound NC(=O)C[C@H](NC(=O)[C@H](CCCNC(=N)N)NC(=O)[C@@H]1CCCN1C(=O)[C@H](CCCNC(=N)N)NC(=O)[C@H](Cc2ccc(F)cc2)NC(=O)[C@H](Cc3c[nH]c4ccccc34)NC(=O)Cc5cccs5)C(=O)N TZCCKCLHNUSAMQ-DUGSHLAESA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910000338 selenium disulfide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D495/14—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
- C07D517/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms in which the condensed system contains three hetero rings
- C07D517/14—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0688—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polyquinolines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1503—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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Abstract
本发明公开了一类硫族元素桥联的紫罗精小分子、聚合物、衍生物及其应用，将紫罗精化合物和硫族元素结合起来，合成硫族元素桥联的紫罗精，此类化合物具有以下特性：1，具有更刚性的骨架和额外的氧化还原中心。2，具有很低的能级差同时具有很低的LUMO能级，是一类很好的电子受体材料并且提高了电子传输性能。3，光学吸收红移至可见光区，使其可应用到光催化领域。本发明成功合成了硫族元素桥联的紫罗精，并将其应用到电致变色和光催化中。本发明通过将此类分子做成聚合物来制备高稳定性的电致变色器件并应用其多氧化还原中心制备有机锂/钠离子电池。
Description
技术领域
本发明属于电致变器件及电池制备领域，涉及一类硫族元素桥联的紫罗精分子及其聚合物、衍生物及其应用，尤其是含硫族元素紫罗精类及联喹啉类小分子及聚合物的合成以及其电致变色器件及有机锂/钠离子电池的应用。
背景技术
随着时代的进步，研发绿色环保、低碳节能的新型功能材料已经成为材料领域的发展趋势。传统纸张及印刷技术浪费了大量森林资源与能源，并对环境造成恶劣的影响，电子墨水和电子纸技术的开发可以解决该问题。电子纸或纸张型显示器由于低能耗、便于携带、可反复擦写等优势，成为目前研究的一个热门领域。并且电子纸或纸张型显示器只有画面转化时才需消耗少量的电能，可以克服发光型显示器耗电量大、不便携带、引起电脑病等诸多缺陷。电致变色材料有很多种,包括紫罗精类、苯胺类、吡咯类和噻吩类等，其中紫罗精类化合物具有良好的电致变色性能，最重要的是其卓越的稳定性，变色后可保持十几年不褪色。
4,4’-联吡啶的N-烷基化衍生物被称作紫罗精，其不同的氧化还原态可以提供电子或接收电子。紫罗精类化合物与其他电至变色材料一样可以在氧化还原过程中发生颜色变化。一般情况下，紫罗精是稳定的二价阳离子形式(RV2+)，在该状态下紫罗精呈现无色，施加一定电压后，紫罗精被还原成一价自由基阳离子形式(RV·+)，由于分子间存在强烈的光电转移，使得单价阳离子颜色最深，继续施加电压，还原成中性态紫罗精类化合物(RV)，其结构十分地特殊，分子内部电子迁移受到阻碍，因此颜色也十分淡。
虽然紫罗精类化合物具有很好的电化学性质，但是其变色情况较为单一，一般只能获得两种颜色之间的变化。同时虽然这类化合物有很低的最低未占轨道(lowestunoccupied molecular orbital，LUMO)能级，但是其共轭程度很低，还原电位仍然较高，具有很大的能隙(band gap)，对可见光吸收很弱，导电性很差，这也极大限制了紫罗精类衍生物在光电领域的应用。
发明内容
为了克服上述现有技术的缺点，本发明的目的在于提供一类硫族元素桥联的紫罗精分子及其聚合物、衍生物及其应用。
为了达到上述目的，本发明采用以下技术方案予以实现：
本发明公开的一类硫族元素桥联的紫罗精小分子，该硫族元素桥联的紫罗精小分子的结构式如下：
其中，R1是胺基烷基或芳基；E是硫、硒或碲；X—是Cl—、Br—、I—、CF3SO2O—、PF6 —、CH3COO—或OTf—。
本发明还公开了含有上述硫族元素桥联的紫罗精小分子的聚合物，该聚合物结构如下：
其中，R2为烷基或芳基，n为大于等于2的正整数。
本发明公开了一类含硫族元素联喹啉的紫罗精分子，该含硫族元素联喹啉的紫罗精分子的结构式如下：
其中，R1甲基、胺基或芳基；E是硫、硒或碲；X—是Cl—、Br—、I—、CF3SO2O—、PF6 —、CH3COO—或OTf-。
本发明还公开了含有上述的含硫族元素联喹啉的紫罗精分子聚合物，该聚合物结构如下：
其中，R2为甲基、胺基或芳基，n为大于等于2的正整数。
本发明还公开了上述的硫族元素桥联的紫罗精小分子、硫族元素桥联的紫罗精小分子的聚合物、含硫族元素联喹啉的紫罗精分子或含硫族元素联喹啉的紫罗精分子聚合物在制备电致变色器件中的应用。
进一步地，制备电致变色器件时，先用紫外固化胶将两片ITO导电玻璃贴合成具有40～60μm厚度空腔的器件基底，将所述的硫族元素桥联的紫罗精小分子、硫族元素桥联的紫罗精小分子的聚合物、含硫族元素联喹啉的紫罗精分子或含硫族元素联喹啉的紫罗精分子聚合物溶解于DMF中，然后加入上述制备好的器件基底的空腔中，密封固化，得到电致变色器件。
本发明还公开了上述的硫族元素桥联的紫罗精小分子、硫族元素桥联的紫罗精小分子的聚合物、含硫族元素联喹啉的紫罗精分子或含硫族元素联喹啉的紫罗精分子聚合物在制备有机锂/钠离子电池中的应用。
进一步地，制备有机锂/钠离子电池时，按照物质A：乙炔黑：PVDF＝6:3:1的质量比配成混合物，将该混合物加入NMP中混匀形成粘性研磨液并均匀涂覆在铜箔上，真空干燥后裁剪，用于制备有机锂/钠离子电池；
其中，物质A为所述的硫族元素桥联的紫罗精小分子、硫族元素桥联的紫罗精小分子的聚合物、含硫族元素联喹啉的紫罗精分子或含硫族元素联喹啉的紫罗精分子聚合物。
本发明还公开了上述的硫族元素桥联的紫罗精小分子、硫族元素桥联的紫罗精小分子的聚合物、含硫族元素联喹啉的紫罗精分子或含硫族元素联喹啉的紫罗精分子聚合物在制备柔性变色电池中的应用。
进一步地，制备柔性变色电池时，按照物质A：PVDF-co-HFP：电解液＝3:4:36的质量比混合，以DMF作溶剂，加热混合均匀后涂在一片ITO导电薄膜上，四周用双面胶固定，制得活性物质层；
将隔膜放置在制备的活性物质层之上，滴加1M的电解液，将锂片用导电胶粘贴在另一片ITO导电薄膜上，将两片ITO导电薄膜用双面胶和紫外固化胶压紧粘贴；
所述电解液由六氟磷酸锂的碳酸乙烯酯、碳酸二甲酯和碳酸甲乙酯按照1:1:1的体积比配制而成；
其中，物质A为所述的硫族元素桥联的紫罗精小分子、硫族元素桥联的紫罗精小分子的聚合物、含硫族元素联喹啉的紫罗精分子或含硫族元素联喹啉的紫罗精分子聚合物。
与现有技术相比，本发明具有以下有益效果：
本发明将紫罗精化合物和硫族元素结合起来，合成硫族元素桥联的紫罗精，此类化合物具有以下特性：1，具有更刚性的骨架和额外的氧化还原中心。2，具有很低的能级差同时具有很低的LUMO能级，是一类很好的电子受体材料并且提高了电子传输性能。3，光学吸收红移至可见光区，使其可应用到光催化领域。由其制成的简易电致变色器件具有低电压，三种不同颜色间(棕色、蓝色及黄色)的变换。由其制得的锂离子电池具有柔性变色的特性。
本发明成功合成了硫族元素桥联的紫罗精，并将其应用到电致变色和有机锂/钠离子电池中。本发明通过将此类分子做成聚合物来制备高稳定性的电致变色器件并应用其多氧化还原中心制备有机锂/钠离子电池。
附图说明
图1含硫族元素紫罗精小分子及聚合物(c＝10-3M)在DMF溶液中的循环伏安图；其中，(a)为化合物2b的循环伏安图；(b)为化合物2c的循环伏安图；(c)为化合物2d的循环伏安图；(d)为化合物5a的循环伏安图；(e)为化合物5b的循环伏安图；(f)为化合物5c的循环伏安图；(g)为化合物5d的循环伏安图；
图2为含硫族元素紫罗精小分子及聚合物(c～10-4M)的紫外-可见吸收光谱；其中，(a)为化合物2b、2c、2d；(b)为5a、5b、5c、5d；
图3(a)含5b的溶液型电致变色器件；不同氧化还原状态下5b的紫外可见吸收光谱及化学还原颜色变化；(b)5b的第一种还原状态；(c)5b的第二种还原状态；
图4(a)含5c的溶液型电致变色器件，不同氧化还原状态下5c的紫外可见吸收光谱及化学还原颜色变化；(b)5c的第一种还原状态；(c)5c的第二种还原状态；
图5(a)含5d的溶液型电致变色器件；不同氧化还原状态下5d的紫外可见吸收光谱及化学还原颜色变化；(b)5d的第一种还原状态；(c)5d的第二种还原状态；
图6(a)2d的首圈放电曲线；右上角为放电到2.3V时的电子顺磁共振谱图；(b)2d放电前以及四次放电电位后的核磁氢谱和(c)原位拉曼光谱；(d)柔性变色电池组装方法(e)从2.6V放电到2.0V的原位反射光谱和(f)电池颜色变化；
图7柔性电池组装示意图。
具体实施方式
为了使本技术领域的人员更好地理解本发明方案，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分的实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当属于本发明保护的范围。
需要说明的是，本发明的说明书和权利要求书及上述附图中的术语“第一”、“第二”等是用于区别类似的对象，而不必用于描述特定的顺序或先后次序。应该理解这样使用的数据在适当情况下可以互换，以便这里描述的本发明的实施例能够以除了在这里图示或描述的那些以外的顺序实施。此外，术语“包括”和“具有”以及他们的任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、系统、产品或设备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。
下面结合附图对本发明做进一步详细描述：
本发明制备的含硫族元素紫罗精类及联喹啉类小分子及聚合物，可通过以下反应方程式的步骤来制备：
1)制备硫族元素桥联紫罗精2和3
化合物1(0.7mmol)溶在DMF中，滴加/胺基烷基氯/胺基烷基溴/胺基烷基碘/芳基溴/芳基碘化物。60℃反应两天。形成的沉淀通过真空抽滤分离，用二氯甲烷洗涤，得到硫族元素桥联紫精2，之后进行应离子交换得到3。R1＝aminoalkyl,aryl；E＝S,Se,Te；X1 -＝Cl—、Br—、I—；X2 —＝CF3SO2O—、PF6 —、CH3COO—、OTf—。
2)制备含硫族元素紫罗精聚合物4和5
化合物1(0.7mmol)和α,α'-dichloro-p-R2/α,α'-dibromo-p-R2/α,α'-diiodo-p-R2溶在DMF中，60℃反应5天。形成的沉淀通过真空抽滤分离，用二氯甲烷洗涤，得到硫族元素桥联紫精聚合物4，之后进行阴离子交换得到5。R2＝alkyl,aryl；E＝S,Se,Te；X1 —＝Cl—、Br—、I—；X2 —＝CF3SO2O—、PF6 —、CH3COO—、OTf—。
3)制备含硫族元素联喹啉类化合物7
在LDA的THF溶液中，–85℃，加入3-溴喹啉，反应两个小时，然后加入氯化铜，通入氧气，然后密封保持在氧气氛围中，室温反应12h，减压旋走THF，加入30mL水,15mL氨水，30mL饱和氯化铵,氯仿萃取，干燥，柱层析分离后即可制得化合物7。反应方程式如下：
4)制备含硫族元素联喹啉类化合物8
向搅拌的化合物5的无水THF(60mL)溶液中滴加n-BuLi(2.5M的己烷溶液，1.68mL，4.2mmol)，在–85℃下搅拌1小时，之后滴加不同的硫族元素化合物{S2Cl2(284mg，2.1mmol)，SeCl2的THF溶液(2.1mmol)，TeCl4(538mg，2.1mmol)},室温反应过夜。在减压下除去挥发物，将残余物溶于H2O(30mL)，NH4OH(25％，15mL)和饱和NH4Cl(15mL)中。将该混合物用氯仿萃取三次，干燥，蒸发溶剂，通过柱色谱法(石油醚/乙酸乙酯，2:1)分离(加入TeCl4的反应需要在旋走THF后加入50mL DCM溶液后加入Na2S水溶液，搅拌至沉淀消失，之后DCM萃取，干燥，DCM中重结晶)，得到硫族元素桥联喹啉(8a,8b,8c)。反应方程式如下：
5)制备含硫族元素联喹啉类紫罗精化合物9和10
化合物5(0.7mmol)溶在DMF中，滴加三氟甲磺酸甲酯/苄基氯/苄基溴/苄基碘/烷基氯/烷基溴/烷基碘/芳基溴/芳基碘化物。60℃反应两天。形成的沉淀通过真空抽滤分离，用二氯甲烷洗涤，得到硫族元素联喹啉类紫罗精化合物9，之后进行应离子交换得到10。R1＝alkyl,aryl；E＝S,Se,Te；X—＝Cl—、Br—、I—、CF3SO2O—、PF6 —、CH3COO—、OTf—。反应方程式如下：
6)制备含硫族元素联喹啉类紫罗精化合物11和12
化合物8(0.7mmol)和α,α'-dichloro-p-R2/α,α'-dibromo-p-R2/α,α'-diiodo-p-R2溶在DMF中，60℃反应5天。形成的沉淀通过真空抽滤分离，用二氯甲烷洗涤，得到硫族元素桥联紫精聚合物11，之后进行阴离子交换得到12。R2＝alkyl,aryl；E＝S,Se,Te；X1 —＝Cl—、Br—、I—；X2 —＝CF3SO2O—、PF6 —、CH3COO—、OTf—。
对本发明上述制得的含硫族元素紫罗精类及联喹啉类小分子及聚合物的物理性质和结构分析，具体如下：
1、含硫族元素紫罗精类及联喹啉类小分子及聚合物的产率、核磁、紫外吸收数据。
5a,E＝S,R2＝xylene,X2 —＝OTf—；a yellow solid.Yield:425mg(72％).1H NMR(400MHz,DMSO):δ10.30(s,2H,PyH),9.45(s,4H,PyH),7.74-7.73(m,4H,o-/m-PhH),6.11(s,4H,CH2)；13C NMR(100MHz,DMSO):δ143.86,143.01,142.24,140.03,135.03,130.21,123.57,122.24,119.03,64.07；elemental analysis calcd(％)for(C20H14F6N2O6S3)n:C40.82,H 2.40,N 4.76；found:C 40.03,H 3.17,N 4.40；UV/vis(in DMF):λmax(ε)＝394nm(2.817×103M-1cm-1).
5b,E＝Se,R2＝xylene,X2 —＝OTf—；a yellow solid.Yield:446mg(70％).1H NMR(400MHz,DMSO):δ10.04(s,2H,PyH),9.45(s,2H,PyH),9.42-9.40(m,2H,PyH),7.73-7.70(m,4H,o-/m-PhH),6.09-6.02(m,4H,CH2)；13C NMR(100MHz,DMSO):δ146.11,145.41,143.97,140.47,135.09,130.34,124.46,122.26,119.06,63.79；elemental analysiscalcd(％)for(C20H14F6N2O6S2Se)n:C 37.81,H 2.22,N 4.41；found:C 37.40,H 3.36,N4.49；UV/vis(in DMF):λmax(ε)＝419nm(2.703×103M-1cm-1).
5c,E＝Te,R2＝xylene,X2 —＝OTf—；a yellow solid.Yield:480mg(70％).1H NMR(400MHz,DMSO):δ9.72-9.71(m,2H,PyH),9.41-9.40(m,2H,PyH),9.35-9.33(m,2H,PyH),7.72-7.68(m,4H,o-/m-PhH),6.03(s,4H,CH2)；13C NMR(100MHz,DMSO):δ151.40,149.17,140.48,139.77,135.17,130.29,130.06,125.53,122.23,119.03,63.20；elementalanalysis calcd(％)for(C20H14F6N2O6S2Te)n:C 35.12,H 2.06,N 4.10；found:C 35.54,H3.35,N 3.97；UV/vis(in DMF):λmax(ε)＝484nm(2.3×103M-1cm-1).
2、基于该硫族元素桥联紫罗精及联喹啉类衍生物制备的电致变色器件的制备
用紫外固化胶将两片ITO导电玻璃贴合成有约50微米厚空腔的器件基底，将硫族元素桥联紫罗精及联喹啉衍生物溶解在DMF中，加入制备好的器件空腔中，密封固化，制得电致变色器件。
3、硫族元素紫罗精类及联喹啉类小分子及聚合物制备有机锂/钠离子电池
含硫族元素紫罗精类及联喹啉类小分子及聚合物：乙炔黑：PVDF＝6:3:1，30mg的混合物中加入0.5mL NMP形成粘性研磨液并均匀涂在铜箔上，80℃真空干燥箱烘6h，冷却后裁剪成直径12mm的圆片。在手套箱中将极片，隔膜，锂片，弹片，垫片，及60μL 1M LiPF6inethylene carbonate(EC)/dimethyl carbonate(DMC)/ethyl methyl carbonate(1:1:1Vol％)电解液封装在CR2032型的纽扣电池中，放置12小时候测试性质。
4、硫族元素紫罗精类及联喹啉类小分子及聚合物的柔性变色电池制作方法
将含硫族元素紫罗精类及联喹啉类小分子及聚合物，PVDF-co-HFP及电解液以3:4:36的比例混合，DMF作溶剂，加热混合均匀后涂在ITO导电薄膜上，四周用双面胶固定，在手套箱中将极片，隔膜及60μL 1M LiPF6in ethylene carbonate(EC)/dimethylcarbonate(DMC)/ethyl methyl carbonate(1:1:1Vol％)电解液放置在一起，将锂片用导电胶粘贴在另一片ITO导电薄膜上，两个极片用双面胶和紫外固化胶压紧粘贴。
实施例1
本发明制备的含硫族元素紫罗精类及联喹啉类小分子及聚合物，通过以下步骤来制备：
(1)制备硫族元素桥联紫罗精2和3
化合物1(0.7mmol)溶在DMF中，滴加/胺基烷基氯/胺基烷基溴/胺基烷基碘/芳基溴/芳基碘化物。60℃反应两天。形成的沉淀通过真空抽滤分离，用二氯甲烷洗涤，得到硫族元素桥联紫精2，之后进行应离子交换得到3。R1＝aminoalkyl,aryl；E＝S,Se,Te；X1 —＝Cl—、Br—、I—；X2 —＝CF3SO2O—、PF6 —、CH3COO—、OTf—。
(2)制备含硫族元素紫罗精聚合物4和5
化合物1(0.7mmol)和α,α'-dichloro-p-R2/α,α'-dibromo-p-R2/α,α'-diiodo-p-R2溶在DMF中，60℃反应5天。形成的沉淀通过真空抽滤分离，用二氯甲烷洗涤，得到硫族元素桥联紫精聚合物4，之后进行阴离子交换得到5。R2＝alkyl,aryl；E＝S,Se,Te；X1 —＝Cl—、Br—、I—；X2 —＝CF3SO2O—、PF6 —、CH3COO—、OTf—。
(3)制备含硫族元素联喹啉类化合物7
在LDA的THF溶液中，–85℃，加入3-溴喹啉，反应两个小时，然后加入氯化铜，通入氧气，然后密封保持在氧气氛围中，室温反应12h，减压旋走THF，加入30mL水,15mL氨水，30mL饱和氯化铵,氯仿萃取，干燥，柱层析分离后即可制得化合物7。
(4)制备含硫族元素联喹啉类化合物8
向搅拌的化合物5的无水THF(60mL)溶液中滴加n-BuLi(2.5M的己烷溶液，1.68mL，4.2mmol)，在–85℃下搅拌1小时，之后滴加不同的硫族元素化合物{S2Cl2(284mg，2.1mmol)，SeCl2的THF溶液(2.1mmol)，TeCl4(538mg，2.1mmol)},室温反应过夜。在减压下除去挥发物，将残余物溶于H2O(30mL)，NH4OH(25％，15mL)和饱和NH4Cl(15mL)中。将该混合物用氯仿萃取三次，干燥，蒸发溶剂，通过柱色谱法(石油醚/乙酸乙酯，2:1)分离(加入TeCl4的反应需要在旋走THF后加入50mL DCM溶液后加入Na2S水溶液，搅拌至沉淀消失，之后DCM萃取，干燥，DCM中重结晶)，得到硫族元素桥联喹啉(8a,8b,8c)。反应方程式如下：
(5)制备含硫族元素联喹啉类紫罗精化合物9和10
化合物5(0.7mmol)溶在DMF中，滴加三氟甲磺酸甲酯/苄基氯/苄基溴/苄基碘/烷基氯/烷基溴/烷基碘/芳基溴/芳基碘化物。60℃反应两天。形成的沉淀通过真空抽滤分离，用二氯甲烷洗涤，得到硫族元素联喹啉类紫罗精化合物9，之后进行应离子交换得到10。R1＝alkyl,aryl；E＝S,Se,Te；X—＝Cl—、Br—、I—、CF3SO2O—、PF6 —、CH3COO—、OTf—。反应方程式如下：
(6)制备含硫族元素联喹啉类紫罗精聚合物11和12
化合物8(0.7mmol)和α,α'-dichloro-p-R2/α,α'-dibromo-p-R2/α,α'-diiodo-p-R2溶在DMF中，60℃反应5天。形成的沉淀通过真空抽滤分离，用二氯甲烷洗涤，得到硫族元素桥联紫精聚合物11，之后进行阴离子交换得到12。R2＝alkyl,aryl；E＝S,Se,Te；X1 —＝Cl—、Br—、I—；X2—＝CF3SO2O—、PF6 —、CH3COO—、OTf—。
采用实施例1制得的硫族元素桥联紫罗精及联喹啉类衍生物制备电致变色器件：用紫外固化胶将两片ITO导电玻璃贴合成有约50微米厚空腔的器件基底，将硫族元素桥联紫罗精及联喹啉衍生物溶解在DMF中，加入制备好的器件空腔中，密封固化，制得电致变色器件。
采用实施例1制得的硫族元素桥联紫罗精及联喹啉类衍生物制备有机锂/钠离子电池：含硫族元素紫罗精类及联喹啉类小分子及聚合物：乙炔黑：PVDF＝6:3:1，30mg的混合物中加入0.5mL NMP形成粘性研磨液并均匀涂在铜箔上，80℃真空干燥箱烘6h，冷却后裁剪成直径12mm的圆片。
在手套箱中将极片、隔膜、锂片、弹片、垫片及60μL 1M LiPF6in ethylenecarbonate(EC)/dimethyl carbonate(DMC)/ethyl methyl carbonate(1:1:1Vol％)电解液封装在CR2032型的纽扣电池中，放置12小时后测试性质。
采用实施例1制得的硫族元素桥联紫罗精及联喹啉类衍生物制备柔性变色电池：将含硫族元素紫罗精类及联喹啉类小分子及聚合物，PVDF-co-HFP及电解液以3:4:36的比例混合，DMF作溶剂，加热混合均匀后涂在ITO导电薄膜上，四周用双面胶固定；在手套箱中将极片、隔膜及60μL 1M LiPF6in ethylene carbonate(EC)/dimethyl carbonate(DMC)/ethyl methyl carbonate(1:1:1Vol％)电解液放置在一起，将锂片用导电胶粘贴在另一片ITO导电薄膜上，两个极片用双面胶和紫外固化胶压紧粘贴。
测试结果参见图1～图7：
图1所展示的是含硫族元素紫罗精2b,2c,2d及其聚合物5a,5b,5c,5d的循环伏安图，表明这些化合物都具有两组可逆的氧化还原中心。
图2所展示的是含硫族元素紫罗精2b,2c,2d(图2中，(a))及其聚合物5a,5b,5c,5d(图2中，(b))的紫外/可见吸收光谱表明随着硫、硒、碲的引入，含硫族元素紫罗精的最大吸收波长红移至可见光区。
图3中，含硫紫罗精聚合物5b在施加0.7V电压时变为蓝色，吸收光谱显示500-800间的吸收逐渐增强，当施加1.2V电压时，颜色变为棕色，500-800间的吸收逐渐减弱。
图4中，含硒紫罗精聚合物5c在施加0.7V电压时变为绿色，吸收光谱显示500-800间的吸收逐渐增强，当施加1.2V电压时，颜色变为黄色，500-800间的吸收逐渐减弱。
图5中，含碲紫罗精聚合物5d在施加0.7V电压时变为紫色，吸收光谱显示500-800间的吸收逐渐增强，当施加1.2V电压时，颜色变为棕色，500-800间的吸收逐渐减弱。
以含碲紫罗精小分子为例，在电池放电过程中(图6中a)，化合物2d经历五种结构变化(由棕色到黑色)，分别对应不同的核磁谱图(图6中b)和拉曼谱图(图6中c)。图6中d为组装的柔性变色电池结构，由六部分组成。在弯折和拉平过程中，由该化合物制备的电池都可以点亮二极管。在对变色电池放电过程中，从开路电压为2.6V降到2.0V过程中，电池颜色由红色逐渐变为深蓝色，表面的反射率呈大范围降低趋势(图6中e)。
图7为组装的柔性变色电池结构，使用导电薄膜作为集流体，在锂片和电致变色活性物质即紫罗精化合物之间放置隔膜和电解液，四周用紫外固化胶或双面胶封装。
以上内容仅为说明本发明的技术思想，不能以此限定本发明的保护范围，凡是按照本发明提出的技术思想，在技术方案基础上所做的任何改动，均落入本发明权利要求书的保护范围之内。
Claims (10)
1.一类硫族元素桥联的紫罗精小分子，其特征在于，该硫族元素桥联的紫罗精小分子的结构式如下：
其中，R1是胺基烷基或芳基；E是硫、硒或碲；X—是Cl—、Br—、I—、CF3SO2O—、PF6 —、CH3COO—或OTf—。
2.含有权利要求1所述的硫族元素桥联的紫罗精小分子的聚合物，其特征在于，该聚合物结构如下：
其中，R2为烷基或芳基，E是硫、硒或碲；X—是Cl—、Br—、I—、CF3SO2O—、PF6 —、CH3COO—或OTf—；n为大于等于2的正整数。
3.一类含硫族元素联喹啉的紫罗精分子，其特征在于，该含硫族元素联喹啉的紫罗精分子的结构式如下：
其中，R1甲基、胺基或芳基；E是硫、硒或碲；X—是Cl—、Br—、I—、CF3SO2O—、PF6 —、CH3COO—或OTf—。
4.含有权利要求3所述的含硫族元素联喹啉的紫罗精分子聚合物，其特征在于，该聚合物结构如下：
其中，R2为甲基、胺基或芳基，E是硫、硒或碲；X—是Cl—、Br—、I—、CF3SO2O—、PF6 —、CH3COO—或OTf—；n为大于等于2的正整数。
5.权利要求1所述的硫族元素桥联的紫罗精小分子、权利要求2所述的硫族元素桥联的紫罗精小分子的聚合物、权利要求3所述的含硫族元素联喹啉的紫罗精分子或权利要求4所述的含硫族元素联喹啉的紫罗精分子聚合物在制备电致变色器件中的应用。
6.如权利要求5所述的应用，其特征在于，制备电致变色器件时，先用紫外固化胶将两片ITO导电玻璃贴合成具有40～60μm厚度空腔的器件基底，将所述的硫族元素桥联的紫罗精小分子、硫族元素桥联的紫罗精小分子的聚合物、含硫族元素联喹啉的紫罗精分子或含硫族元素联喹啉的紫罗精分子聚合物溶解于DMF中，然后加入上述制备好的器件基底的空腔中，密封固化，得到电致变色器件。
7.权利要求1所述的硫族元素桥联的紫罗精小分子、权利要求2所述的硫族元素桥联的紫罗精小分子的聚合物、权利要求3所述的含硫族元素联喹啉的紫罗精分子或权利要求4所述的含硫族元素联喹啉的紫罗精分子聚合物在制备有机锂/钠离子电池中的应用。
8.如权利要求7所述的应用，其特征在于，制备有机锂/钠离子电池时，按照物质A：乙炔黑：PVDF＝6:3:1的质量比配成混合物，将该混合物加入NMP中混匀形成粘性研磨液并均匀涂覆在铜箔上，真空干燥后裁剪，用于制备有机锂/钠离子电池；
其中，物质A为所述的硫族元素桥联的紫罗精小分子、硫族元素桥联的紫罗精小分子的聚合物、含硫族元素联喹啉的紫罗精分子或含硫族元素联喹啉的紫罗精分子聚合物。
9.权利要求1所述的硫族元素桥联的紫罗精小分子、权利要求2所述的硫族元素桥联的紫罗精小分子的聚合物、权利要求3所述的含硫族元素联喹啉的紫罗精分子或权利要求4所述的含硫族元素联喹啉的紫罗精分子聚合物在制备柔性变色电池中的应用。
10.如权利要求9所述的应用，其特征在于，制备柔性变色电池时，按照物质A：PVDF-co-HFP：电解液＝3:4:36的质量比混合，以DMF作溶剂，加热混合均匀后涂在一片ITO导电薄膜上，四周用双面胶固定，制得活性物质层；
将隔膜放置在制备的活性物质层之上，滴加1M的电解液，将锂片用导电胶粘贴在另一片ITO导电薄膜上，将两片ITO导电薄膜用双面胶和紫外固化胶压紧粘贴；
所述电解液由六氟磷酸锂的碳酸乙烯酯、碳酸二甲酯和碳酸甲乙酯按照1:1:1的体积比配制而成；
其中，物质A为所述的硫族元素桥联的紫罗精小分子、硫族元素桥联的紫罗精小分子的聚合物、含硫族元素联喹啉的紫罗精分子或含硫族元素联喹啉的紫罗精分子聚合物。
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| CN111285883A (zh) * | 2020-04-01 | 2020-06-16 | 西安交通大学 | 一类噻吩基含硫族元素紫罗精及其联喹啉衍生物和应用 |
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| CN111285883A (zh) * | 2020-04-01 | 2020-06-16 | 西安交通大学 | 一类噻吩基含硫族元素紫罗精及其联喹啉衍生物和应用 |
| CN111285883B (zh) * | 2020-04-01 | 2022-02-15 | 西安交通大学 | 一类噻吩基含硫族元素紫罗精及其联喹啉衍生物和应用 |
| CN112209955A (zh) * | 2020-10-15 | 2021-01-12 | 西安交通大学 | 一类碳硼烷紫罗精衍生物及其金属超分子聚合物、合成方法和应用 |
| CN112209955B (zh) * | 2020-10-15 | 2021-08-13 | 西安交通大学 | 一类碳硼烷紫罗精衍生物及其金属超分子聚合物、合成方法和应用 |
| CN113512051A (zh) * | 2021-06-25 | 2021-10-19 | 西安交通大学 | 一类硼氮杂苯并联噻吩紫精衍生物的制备方法及其在电致变色器件中的应用 |
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