CN114524764B - Novel asymmetric viologen compound and preparation method and application thereof - Google Patents
Novel asymmetric viologen compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN114524764B CN114524764B CN202210150454.1A CN202210150454A CN114524764B CN 114524764 B CN114524764 B CN 114524764B CN 202210150454 A CN202210150454 A CN 202210150454A CN 114524764 B CN114524764 B CN 114524764B
- Authority
- CN
- China
- Prior art keywords
- compound
- viologen compound
- viologen
- tpy
- vio
- 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.)
- Active
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims description 18
- 230000002441 reversible effect Effects 0.000 claims abstract description 11
- 230000000638 stimulation Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000002468 redox effect Effects 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 17
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001450 anions Chemical class 0.000 abstract description 5
- 239000011263 electroactive material Substances 0.000 abstract description 4
- 230000002950 deficient Effects 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 229940125898 compound 5 Drugs 0.000 description 7
- 230000033116 oxidation-reduction process Effects 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229940126214 compound 3 Drugs 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- -1 terpyridine compound Chemical class 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 3
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940125773 compound 10 Drugs 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical class FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-P 4-pyridin-1-ium-4-ylpyridin-1-ium Chemical compound C1=[NH+]C=CC(C=2C=C[NH+]=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-P 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 150000004292 cyclic ethers Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [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 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 150000005839 radical cations Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000004984 smart glass Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- B01J35/33—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a novel asymmetric viologen compound which consists of receptor 4,4' -bipyridine, different donor groups and different counter anions, and has the structural formula ofThe invention also discloses a synthesis method of the asymmetric viologen compound, which mainly comprises the steps of combining different electron-rich donor groups with electron-deficient viologen biscations, and changing different counter anions to obtain an asymmetric viologen compound with different counter anions; the viologen compound has relatively stable electrochromic performance, and under the condition of electric stimulation, the viologen compound generates reversible oxidation-reduction reaction to be accompanied with rich color change, so that the low-voltage driven electrochromic device with rich color change can be prepared by taking the viologen compound as an electroactive material.
Description
Technical Field
The invention belongs to the field of organic photoelectric information materials and devices, and particularly relates to a novel asymmetric viologen compound, a preparation method and application thereof.
Background
Materials that tend to change color reversibly under electrochemical stimulation are known as electrochromic materials, a phenomenon known as Electrochromic (EC). These materials have been widely used in electrochromic devices (ECD) for antiglare rearview mirrors or low power consumption displays. Electrochromic (EC) materials can be broadly divided into two broad categories, inorganic materials and organic materials. Inorganic materials include transition metals and metal oxides, prussian blue series, lanthanide series complexes, and the like. Organic materials include viologen derivatives (1, 1 '-dialkyl 4,4' -bipyridinium), TTF (tetrathiafulvalene) derivatives, TCNQ (tetracyanoquinoline dimethane) derivatives, quinones, conductive polymers, wherein the conductive polymers include polythiophene (PTh), polyaniline (PANI), polypyrrole (PPy). The most important property of these materials is that they can exhibit a color change between oxidation/reduction states under low voltage driving. Furthermore, the chemical structural design of EC materials plays a crucial role in determining their light absorption capacity at different wavelengths, making them good candidates for low power applications.
Among these classes of materials, organic electrochromic materials are widely favored because of their good optical properties, rich colors, fast color conversion, good cycle reversibility, easy modification of structure, and low cost. Wherein the organic micromolecule viologen has the advantages of easy modification of chemical structure, relatively rich oxidation-reduction state, good oxidation-reduction reversibility and excellent electron accepting capability. Therefore, the materials are also widely used in the application fields of energy-saving smart windows, energy storage devices and the like. While the introduction of a number of electron withdrawing groups into viologen has been previously reported, it was found that electron withdrawing groups enhance electron deficiency of viologen, reducing the kinetic stability of electrochromic devices. It is therefore desirable to enhance the structural stability of viologen compounds by introducing different electron rich donor groups into the viologen, utilizing electron transfer between the electron donor and electron acceptor units; the purple fine compound is used as an electrochromic active material, so that an electrochromic device with large area and rich color change can be developed, and the application of the purple fine compound in an intelligent window can be further realized.
Disclosure of Invention
In order to further improve the application of the viologen compound in electrochromic materials such as intelligent windows and the like and realize the reversible change of multiple colors under lower voltage, the invention provides a novel asymmetric viologen compound and a preparation method and application thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the novel asymmetric viologen compound is prepared by introducing a terpyridine compound onto 4,4 '-bipyridine, then obtaining the viologen compound with different counter anions through ion exchange, and the D-A-like structure is formed by utilizing the electron-rich characteristic of the donor terpyridine and the electron-deficient characteristic of the acceptor 4,4' -bipyridine, so that the stability of the viologen compound is enhanced, and the novel asymmetric viologen compound has good reversible redox; under the action of electric stimulation, the novel asymmetric viologen compound generates reversible oxidation-reduction reaction and accompanies color change, and is used as an active material, and is doped with a proper electrolyte to prepare an electrochromic device with obvious color change. Through device optimization, a large-area electrochromic device with rich color change and good circulation stability under low voltage can be manufactured, and further the application of the device in an intelligent window is realized.
The invention discloses a novel asymmetric viologen compound which is Tpy-Vio-X - The structural general formula is shown as follows:
wherein, the liquid crystal display device comprises a liquid crystal display device,
X 1 - is I - 、Cl - 、TFSI - 、PF 6 - 、Br - 、ClO 4 - Or BF 4 - Any one of the following;
X 2 - is I - 、Cl - 、TFSI - 、PF 6 - 、Br - 、ClO 4 - Or BF 4 - Any one of the following;
n is 0 or 1;
r may be independently selected from branched, straight, cyclic ether chains or cyclic alkyl chains having a positive integer number of carbon atoms.
The synthetic route of the novel asymmetric viologen compound is divided into two paths of two different products of n=0 and n=1, and when n=0, the novel asymmetric viologen compound product is marked as Tpy-Vio-1-X - The method comprises the steps of carrying out a first treatment on the surface of the When n=1, the novel asymmetric viologen compound products are marked as Tpy-Vio-2-X - 。
The Tpy-Vio-1-X - And said Tpy-Vio-2-X - The synthetic route is as follows, wherein X comprises X 1 And X 2 ：
The specific synthesis steps of the novel asymmetric viologen compound are as follows:
(1) Preparation of compound 5: reflux reacting 4,4' -bipyridine and 1-chloro-2, 4-dinitrobenzene in acetonitrile, ethanol or acetone solvent for less than 72h, cooling to room temperature, filtering, spin-drying filtrate, washing with acetone for 2 times, washing with diethyl ether for 2 times, and vacuum drying to obtain a compound 5;
(2) Preparation of compound 3: dissolving a compound 1 in methanol, then adding a compound 2, then adding a corresponding 15% potassium hydroxide aqueous solution, adding a corresponding ammonia water, and stirring at 10-30 ℃ for less than 3 days; filtering to obtain filter cakes, respectively washing 3 times with alcohol and deionized water, completely dissolving the filter cakes with dichloromethane, extracting with saturated sodium bicarbonate aqueous solution, concentrating until the dichloromethane is just dissolved, and adding a large amount of methanol or ethanol for sedimentation. Filtering to obtain a filter cake, washing with methanol or ethanol for three times, and vacuum drying to obtain a compound 3;
(3) Preparation of Compound 4: compound 3, palladium carbon with the mass fraction of 10%, 10mL of hydrazine hydrate in ethanol, and refluxing and stirring for 24h; cooling to room temperature, filtering to remove palladium carbon, and removing solvent by rotary evaporation to obtain a compound 4;
(4) Preparation of Compound 6: reflux reaction of the compound 4 and the compound 5 in a mixed solvent of alcohol and deionized water for 48-84 h; cooling to room temperature, removing the solvent by rotary evaporation, adding a small amount of benign solvent to completely dissolve the solid, and then adding a large amount of poor solvent to settle to obtain a compound 6;
(5) Compound Tpy-Vio-1-X - Is prepared from the following steps: the compound 6 reacts with halogenated compounds in DMSO, acetonitrile, DMF, alcohol and other solvents respectively for 12-24 h at 30-45 ℃ under nitrogen atmosphere; after the reaction is finished, spin-drying to remove the solvent; dissolving the solid by using a benign solvent, adding perchlorate, fluorophosphate, halogenated salt, tetrafluoroborate or bis (trifluoromethanesulfonyl) imide salt, and stirring for 5-24 hours at room temperature; after the reaction is finished, filtering and recrystallizing to obtain a compound Tpy-Vio-1-X - ；
(6) Preparation of Compound 9: tetra (triphenylphosphine) palladium is used as a catalyst, the compound 7 and the compound 8 are dissolved in toluene solvent, and reflux is carried out for 12-36 h under the condition of nitrogen; cooling to room temperature, adding saturated sodium chloride aqueous solution for extraction, drying the organic solvent with anhydrous sodium sulfate, and removing the solvent by rotary evaporation to obtain a compound 9;
(7) Preparation of compound 10: 10mL of hydrazine hydrate of the compound 9, 10% palladium carbon by mass fraction is refluxed and stirred in ethanol for 24h; cooling to room temperature, filtering to remove palladium carbon, and removing solvent by rotary evaporation to obtain a compound 10;
(8) Preparation of Compound 11: reflux reaction of the compound 10 and the compound 5 in a mixed solvent of alcohol and deionized water for 48-84 h; cooling to room temperature, removing the solvent by rotary evaporation, adding a small amount of benign solvent to completely dissolve the solid, and then adding a large amount of poor solvent to settle to obtain a compound 11;
(9) Compound Tpy-Vio-2-X - Is prepared from the following steps: the compound 11 reacts with halogenated compounds in DMSO, acetonitrile, DMF, alcohol and other solvents respectively for 12-24 hours at 30-45 ℃ under nitrogen atmosphere; after the reaction is finished, spin drying and removingRemoving the solvent; dissolving the solid by using a benign solvent, adding perchlorate, fluorophosphate, halogenated salt, tetrafluoroborate or bis (trifluoromethanesulfonyl) imide salt, and stirring for 5-24 hours at room temperature; after the reaction is finished, filtering and recrystallizing to obtain a compound Tpy-Vio-2-X - 。
With the novel asymmetric viologen compound Tpy-Vio-1-X - Or Tpy-Vio-2-X - As an electroactive material, an electrochromic solution is prepared by doping a suitable electrolyte (imidazole salt, lithium salt) in a suitable solvent (DMF, acetonitrile, DMSO, acetone), and then an electrochromic device is prepared.
The novel asymmetric viologen compound provided by the invention has the advantages of rich oxidation-reduction state, good electron accepting capability, easy change of substituent groups and the like, so that the structure of the viologen can be diversified, and the polychromance and the multifunctionality are further realized.
The novel asymmetric viologen compound can be prepared into a material with electrochromic and electrochromic luminescence after being coupled with metal by introducing metal, so that a dual-function device is obtained.
The novel asymmetric viologen compound can be used as a color indicator and connected with an energy storage device, so that the charge and discharge states of the novel asymmetric viologen compound can be directly observed.
The novel asymmetric viologen compound can be used for preparing an organic flow battery by utilizing the electron deficiency characteristic and the reversible oxidation-reduction characteristic of the novel asymmetric viologen compound.
The novel asymmetric viologen compound disclosed by the invention is used as a super capacitor by utilizing the acceptable electronic characteristics of the asymmetric viologen compound.
The novel asymmetric viologen compound can be used as an electron transfer catalyst by utilizing the reversible electron transfer reaction inside the asymmetric viologen compound.
The novel class of asymmetric viologen compounds of the present invention can be used to modify metals by coupling the metals to the terpyridine moiety of the asymmetric viologen compound, thereby being useful as corrosion inhibitors for microbial effects.
The novel asymmetric viologen compound disclosed by the invention can be used as an energy storage device by utilizing ideal electron accepting capability and good oxidation-reduction behavior of viologen.
The beneficial effects of the invention are as follows: introducing a terpyridine compound onto 4,4' -bipyridine, and then obtaining a novel asymmetric viologen compound with different counter anions through ion exchange, wherein the novel asymmetric viologen compound has excellent electrochemical and photophysical properties, and is used as an electroactive material and doped with a proper electrolyte to prepare an electrochromic device; under the action of electric stimulation, oxidation-reduction reversible reaction occurs, and the color of the device is obviously and abundantly changed. The novel asymmetric viologen compound has simple synthesis steps, a plurality of oxidation-reduction states and can realize color change by applying low voltage. Through device optimization, a large-area electrochromic device with rich color change and good circulation stability can be manufactured, and further the application of the device in an intelligent window is realized.
Drawings
FIG. 1a is a schematic diagram of Tpy-Vio-1-X in example 2 - (X 1 ＝Cl,X 2 Cyclic voltammogram negative oxidation peak of =i);
FIG. 1b is a schematic diagram of Tpy-Vio-1-X in example 2 - (X 1 ＝Cl,X 2 Cyclic voltammogram positive oxidation peak of =i);
FIG. 2 shows the use of Tpy-Vio-1-X in example 3 - (X 1 ＝Cl,X 2 =i) making an electrochromic map of the device at the operating voltage;
FIG. 3a shows the use of Tpy-Vio-1-X in example 4 - (X 1 ＝Cl,X 2 Absorption spectrum of the device made by =i) under applied negative pressure;
FIG. 3b shows the use of Tpy-Vio-1-X in example 4 - (X 1 ＝Cl,X 2 An absorption spectrum of the voltage of the device made by =i) after a period of continuous application;
FIG. 4 shows the use of Tpy-Vio-1-X in example 5 - (X 1 ＝Cl,X 2 Device made by =i) under application of negative pressureA transmittance change map of (2);
FIG. 5 shows the use of Tpy-Vio-1-X in example 6 - (X 1 ＝Cl,X 2 Current consumption profile of the device made =i) under application of negative voltage;
FIG. 6 shows the use of Tpy-Vio-1-X in example 7 - (X 1 ＝Cl,X 2 Test of the cycling stability of the device made =i) under applied negative pressure.
Detailed Description
The following describes in detail the embodiments of the present invention, which are implemented on the premise of the technical solution of the present invention, and give detailed embodiments and specific operation procedures, but the scope of protection of the present invention is not limited to the following examples.
Compound Tpy-Vio-1-X - And Tpy-Vio-2-X - Has similar properties, multiple redox states, good redox reversibility, sensitivity to low voltage response, and similar synthesis steps, similar photophysical properties, and Tpy-Vio-1-X - (X 1 ＝Cl,X 2 The following description will be given in detail by taking =i) as an example.
Example 1: tpy-Vio-1-X - (X 1 ＝Cl,X 2 Preparation of =i)
(1) Preparation of compound 5: 1-chloro-2, 4-dinitrobenzene (300 mg,1.49 mmol) and 4,4' -bipyridine (348 mg,2.20 mmol) were reacted with reflux in anhydrous acetonitrile for 48h, after the reaction was completed, cooled to room temperature, filtered, the filtrate was dried by spin-drying and washed 3 times with acetone and diethyl ether, then filtered and dried under vacuum to give compound 5. Yield: 70%.
1 H NMR(400MHz,D 2 O)δ(ppm):9.30(d,J＝2.5Hz,1H),9.16(d,J＝7.1Hz,2H),8.84(dd,J＝8.7,2.5Hz,1H),8.76-8.73(m,2H),8.59(d,J＝7.1Hz,2H),8.18(d,J＝8.7Hz,1H),7.95-7.91(m,2H)。
(2) Preparation of compound 3: compound 1 (500 mg,3.31 mmol) was completely dissolved in methanol, then compound 2 (800 mg,6.62 mmol) was added, 15mL of 15% KOH aqueous solution was added, and 15mL of aqueous ammonia was added and stirred at 25℃for 3 days; after the reaction, a large amount of black solid appears, the precipitate is collected by vacuum filtration, and is washed 3 times by methanol and water respectively, then the precipitate is dissolved by methylene dichloride, the solution is transferred to a separating funnel, saturated sodium bicarbonate aqueous solution is added for two times, the organic layer is transferred to a conical flask to be dried by anhydrous sodium sulfate, the solution is concentrated until a large amount of methanol is just dissolved, and a large amount of precipitate is precipitated by standing, and after filtration, a filter cake is placed into a vacuum drying box to be dried for 12 hours, and the compound 3 is obtained by vacuum drying. Yield: 45%.
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.78(d,J＝2.9Hz,2H),8.76(m,2H),8.73-8.70(m,2H),8.42-8.38(m,2H),8.10-8.05(m,2H),7.96-7.91(m,2H),7.41(m,2H)。
(3) Preparation of Compound 4: compound 3 (400 mg,1.10 mmol), 10% mass fraction palladium on carbon (80 mg), hydrazine hydrate (8 mL) in ethanol under reflux stirring for 24h; cooling to room temperature, filtering to remove palladium carbon, removing solvent by rotary evaporation, removing hydrazine hydrate difficultly, adding water and dichloromethane for extraction, washing twice with saturated salt water, drying with anhydrous sodium sulfate, and rotary drying the solvent to obtain the compound 4. Yield: 90%.
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.75(d,J＝4.0Hz,2H),8.71(s,2H),8.69(d,J＝8.0Hz,2H),7.92–7.87(m,2H),7.83–7.79(m,2H),7.37(m,2H),6.85–6.81(m,2H),5.32(s,2H)。
(4) Preparation of Compound 6: reflux reaction of compound 4 (324 mg,0.43 mmol) and compound 5 (141 mg,0.39 mmol) in a mixed solvent of ethanol and deionized water for 84h; cooling to room temperature, removing the solvent by rotary evaporation, adding a small amount of methanol to completely dissolve the solid, and adding a large amount of acetone and ethyl acetate to settle to obtain the compound 6. Yield: 50%.
1 H NMR(400MHz,DMSO-d 6 )δ(ppm):9.62(d,J＝6.4Hz,1H),8.94(d,J＝5.0Hz,1H),8.87-8.83(m,2H),8.80(d,J＝3.7Hz,1H),8.73(d,J＝8.2Hz,1H),8.38(d,J＝8.4Hz,1H),8.18(m,2H),8.09(t,J＝7.1Hz,1H),7.60-7.56(m,1H)。
(5) Compound Tpy-Vio-1-X - Preparation of (x=cl, I): compound 6 (0.5 mmol,300 mg) and methyl iodide (8.0 mmol,0.5 mL) were reacted under an acetonitrile solvent and nitrogen atmosphere at 43℃for 24h; after the reaction is finished, spin-drying the reaction solution, just dissolving the reaction solution with DMSO, adding a proper amount of acetone, standing to separate out precipitate, filtering, and vacuum drying a filter cake to obtain a compound Tpy-Vio-1-X - (X 1 ＝Cl,X 2 =i). Yield: 60%.
1 H NMR(400MHz,DMSO-d 6 )δ(ppm):9.79(s,1H),9.66(s,1H),9.35(s,2H),8.96(d,J＝30.5Hz,9H),8.50(s,2H),8.36(s,2H),8.23(d,J＝7.0Hz,2H),7.95(s,1H),7.81(s,2H),4.49(s,3H)。
13 C NMR(100MHz,DMSO-d 6 )δ(ppm):156.5,155.1,153.8,151.6,149.9,148.2,145.9,143.3,141.0,140.8,138.1,129.3,126.3,125.8,125.2,122.6,121.6,118.8,40.0。
Example 2: tpy-Vio-1-X - (X 1 ＝Cl,X 2 Cyclic voltammetry test of =i)
Tpy-Vio-1-X - (X 1 ＝Cl,X 2 The cyclic voltammetry test of =i) uses a three-electrode system, the counter electrode is a platinum wire electrode, the working electrode is a palladium carbon electrode, and the reference electrode is Ag/AgNO 3 . A solution of tetrabutylammonium hexafluorophosphate in DMF (0.1M) was used as electrolyte. The scanning speed was 100 mV.s -1 。
Tpy-Vio-1-X - (X 1 ＝Cl,X 2 Cyclic voltammograms of =i) are shown in fig. 1. As can be seen from fig. 1a, the compound shares three pairs of reversible redox peaks at the negative level, wherein two pairs of reversible redox peaks at a negative potential and a low potential correspond to the reduction potential of viologen biscationate to obtain one electron and two electrons, and one pair of reversible redox peaks at a high potential corresponds to the generation of nitrogen atom-available electrons on terpyridine, and fig. 1b shows that the oxidation peak of the positive electrode of the compound corresponds to the loss of one electron by iodide ion and the loss of two electrons by three electrons.
Example 3: by Tpy-Vio-1-X - (X 1 ＝Cl,X 2 Device made by =i) color change under electrical stimulation
Tpy-Vio-1-X - (X 1 ＝Cl,X 2 Cyclic voltammograms of the =i) devices are shown in fig. 2. As can be seen from the figure, the electrochromic device prepared by doping the compound serving as an electroactive material with a proper electrolyte shows orange color when no voltage is applied, and the initial voltage V is applied 1＝ After 1.2V, the device turns yellow-green in color and voltage V is applied continuously 2＝ After 1.8v, the device color changed to dark green.
Example 4: by Tpy-Vio-1-X - (X 1 ＝Cl,X 2 Absorption spectrum test of devices made by =i) under applied operating voltage
The ultraviolet-visible spectrophotometer is used in combination with an electrochemical analyzer, the electrochemical analyzer applies voltage to the device, and the ultraviolet-visible spectrophotometer is used for measuring the change of the absorption intensity of the device under different voltages.
By Tpy-Vio-1-X - (X 1 ＝Cl,X 2 Device made of =i) is applied with lower voltage V 1 As the optical characteristics of the device change, as can be seen from fig. 3a, a more pronounced absorption peak occurs at 721nm compared to 0V, when an electron from the biscationic state is converted into the radical cation state; continuing to apply voltage V 2 At 556nm, the absorption peak is blue shifted by 35nm, and the free radical cation state is changed into a neutral state. As can be seen from fig. 3b, the absorption intensity is not increased after the voltage is continuously applied for a period of time, and the voltage is stable.
Example 5: by Tpy-Vio-1-X - (X 1 ＝Cl,X 2 Transmittance test of devices made by =i) under applied operating voltage
The ultraviolet-visible spectrophotometer and the electrochemical analyzer are simultaneously used for measuring the change of the transmittance of the device under different voltages.
By Tpy-Vio-1-X - (X 1 ＝Cl,X 2 The absorption spectrum of the device made of =i) under the applied operating voltage is shown in fig. 4. As can be seen, when a lower voltage V is applied 1 At 679nm, the maximum transmittance is 31%, which corresponds to Tpy-Vio-1-X - (X 1 ＝Cl,X 2 =i) a radical cationic state of one electron; continuing to increase voltage V 2 At 679nm, the maximum transmittance is 60%, which corresponds to Tpy-Vio-1-X - (X 1 ＝Cl,X 2 =i) yields the neutral state of both electrons.
Example 6: by Tpy-Vio-1-X - (X 1 ＝Cl,X 2 Current consumption test and cycle stability test of devices made by =i) under applied operating voltage
By Tpy-Vio-1-X - (X 1 ＝Cl,X 2 The current consumption test of the device made by =i) under the application of the operating voltage is shown in fig. 5. By Tpy-Vio-1-X - (X 1 ＝Cl,X 2 Cyclic stability test of the device made =i) under applied operating voltage is shown in fig. 6. As can be seen from the graph, the transmittance of the device at 679nm was 92% in the initial state, and the transmittance became 35% when the device was completely colored after the operating voltage was applied; after a coloring cycle of 4 hours, the transmittance at the time of coloring can reach 90%, the transmittance at the time of fading is 40%; the transmittance at coloring was reduced by 0.6% compared to the initial test data. The device has a coloring time of 10s, a fading time of 9s and a coloring efficiency of 95% under the working voltage; it can be seen that the cyclic stability of the device is better.
Claims (3)
1. An asymmetric viologen compound is characterized by having a chemical structural formula:
2. the method for preparing the asymmetric viologen compound as claimed in claim 1, wherein the synthetic route of the compound is as follows,
3. use of an asymmetric viologen compound of a class of claim 1 where reversible redox properties can occur under electrical stimulation to be used in the preparation of electrochromic devices.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210150454.1A CN114524764B (en) | 2022-02-18 | 2022-02-18 | Novel asymmetric viologen compound and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210150454.1A CN114524764B (en) | 2022-02-18 | 2022-02-18 | Novel asymmetric viologen compound and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114524764A CN114524764A (en) | 2022-05-24 |
| CN114524764B true CN114524764B (en) | 2023-08-18 |
Family
ID=81622113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210150454.1A Active CN114524764B (en) | 2022-02-18 | 2022-02-18 | Novel asymmetric viologen compound and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114524764B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104292151A (en) * | 2013-07-16 | 2015-01-21 | 中国科学院上海有机化学研究所 | Novel viologen compounds and preparation method thereof |
| JP2017206499A (en) * | 2016-05-12 | 2017-11-24 | キヤノン株式会社 | Organic compound, electrochromic compound, electrochromic device having the same, optical filter, lens unit, imaging device and window material |
| CN109563351A (en) * | 2016-07-19 | 2019-04-02 | 国立研究开发法人物质·材料研究机构 | A kind of compound containing organic/metal hybrid polymer and ionic liquid, electrochromic device and their manufacturing method using the compound |
| CN110105336A (en) * | 2019-05-30 | 2019-08-09 | 华南理工大学 | Viologen derivative electrochromic material and preparation method thereof |
| CN110642853A (en) * | 2019-10-16 | 2020-01-03 | 南方科技大学 | Electrochromic device and application thereof |
| CN110845477A (en) * | 2019-11-20 | 2020-02-28 | 南京邮电大学 | Novel symmetrical viologen compound and preparation method and application thereof |
| CN111183392A (en) * | 2017-10-10 | 2020-05-19 | 佳能株式会社 | Electrochromic element, optical filter, lens unit, image pickup apparatus, and window member |
| CN111793062A (en) * | 2020-07-30 | 2020-10-20 | 南京邮电大学 | Novel asymmetric viologen compound and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6630481B2 (en) * | 2001-02-28 | 2003-10-07 | Council Of Scientific And Industrial Research Of India | Viologen linked acridine based molecule and process for the preparation thereof |
| KR100965225B1 (en) * | 2008-03-06 | 2010-06-22 | 연세대학교 산학협력단 | Electrochromic viologens with asymmetric structure and device therefrom |
| EP3115433B1 (en) * | 2015-07-08 | 2018-10-03 | Essilor International | Electrochromic compounds and optical articles containing them |
| US10310350B2 (en) * | 2016-05-12 | 2019-06-04 | Canon Kabushiki Kaisha | Organic compound, electrochromic compound, and electrochromic element, optical filter, lens unit, imaging device, and window component having same |
-
2022
- 2022-02-18 CN CN202210150454.1A patent/CN114524764B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104292151A (en) * | 2013-07-16 | 2015-01-21 | 中国科学院上海有机化学研究所 | Novel viologen compounds and preparation method thereof |
| JP2017206499A (en) * | 2016-05-12 | 2017-11-24 | キヤノン株式会社 | Organic compound, electrochromic compound, electrochromic device having the same, optical filter, lens unit, imaging device and window material |
| CN109563351A (en) * | 2016-07-19 | 2019-04-02 | 国立研究开发法人物质·材料研究机构 | A kind of compound containing organic/metal hybrid polymer and ionic liquid, electrochromic device and their manufacturing method using the compound |
| CN111183392A (en) * | 2017-10-10 | 2020-05-19 | 佳能株式会社 | Electrochromic element, optical filter, lens unit, image pickup apparatus, and window member |
| CN110105336A (en) * | 2019-05-30 | 2019-08-09 | 华南理工大学 | Viologen derivative electrochromic material and preparation method thereof |
| CN110642853A (en) * | 2019-10-16 | 2020-01-03 | 南方科技大学 | Electrochromic device and application thereof |
| CN110845477A (en) * | 2019-11-20 | 2020-02-28 | 南京邮电大学 | Novel symmetrical viologen compound and preparation method and application thereof |
| CN111793062A (en) * | 2020-07-30 | 2020-10-20 | 南京邮电大学 | Novel asymmetric viologen compound and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Enhanced electrochromic properties of terpyridine-attached asymmetric viologen with high transmittance and switching stability;Gopal Balamurugan et al.;《Solar Energy Materials and Solar Cells》;第246卷;第1-8页（110714） * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114524764A (en) | 2022-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chang et al. | Conjugation-extended viologens with thiophene derivative bridges: near-infrared electrochromism, electrofluorochromism, and smart window applications | |
| JP2016506379A (en) | Cobalt complex | |
| CN114605620B (en) | Electrochromic polymer, preparation method thereof and electrochromic film | |
| CN114907551B (en) | Red electrochromic polymer, preparation method, film and device | |
| CN106463274B (en) | Photo-electric conversion element, dye-sensitized solar cell, metal complex dye, pigment solution and terpyridyl compounds or its carboxylate | |
| Liu et al. | Efficient metal-free sensitizers bearing circle chain embracing π-spacers for dye-sensitized solar cells | |
| Wu et al. | Novel organic dyes based on diarylmethylene-bridged triphenylamine for dye-sensitized solar cells | |
| Zhang et al. | Visible and infrared electrochromism of bis (2-(2-(2-hydroxyethoxy) ethoxy) ethyl) viologen with sodium carboxymethyl chitosan-based hydrogel electrolytes | |
| Sydam et al. | Enhanced electrochromic write–erase efficiency of a device with a novel viologen: 1, 1′-bis (2-(1H-indol-3-yl) ethyl)-4, 4′-bipyridinium diperchlorate | |
| CN110845477A (en) | Novel symmetrical viologen compound and preparation method and application thereof | |
| Kuai et al. | Self-assembled flexible metallo-supramolecular film based on Fe (II) ion and triphenylamine-subsituted alkyl terpyridine towards electrochromic application | |
| CN103329343A (en) | Photoelectric conversion element | |
| Halder et al. | Vis-to-NIR electrochromism and bright-to-dark electrofluorochromism in a triazine and thiophene-based three-dimensional covalent polymer | |
| Halder et al. | Fe (II)-based dual function metallo-supramolecular polymer with thiazolothiazole spacer for high-performance electrochromic supercapattery | |
| CN111793062B (en) | Novel asymmetric viologen compound and preparation method and application thereof | |
| CN114524764B (en) | Novel asymmetric viologen compound and preparation method and application thereof | |
| Zhuang et al. | Electrochromism and Electrofluorochromism based on Viologen Derivative with 1, 10‐Phenanthroline Moiety for Multicolor Large‐Area and Patterned Display | |
| CN116874747A (en) | Electrochromic polymer, preparation method thereof and electrochromic polymer film | |
| Wang et al. | A novel p/n-dopable electrochromic electrode material based on P (TPACz)/WO3 coralloid porous nanocomposite | |
| CN112592373B (en) | Ionic Iridium (III) complex containing viologen unit and preparation method and application thereof | |
| Zhang et al. | A fast-response electrochromic device based on a composite gel film comprising triphenylamine derivatives and WO 3 | |
| CN113072688B (en) | Novel viologen polymer and preparation method and application thereof | |
| CN107964091B (en) | Multifunctional bipolar conductive polymer and preparation method and application thereof | |
| CN115536578B (en) | Aromatic ester substituted viologen black electrochromic compound and preparation method and application thereof | |
| CN116655632A (en) | Purple essence compound and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |