CN114524764A - 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
- CN114524764A CN114524764A CN202210150454.1A CN202210150454A CN114524764A CN 114524764 A CN114524764 A CN 114524764A CN 202210150454 A CN202210150454 A CN 202210150454A CN 114524764 A CN114524764 A CN 114524764A
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- Prior art keywords
- compound
- viologen
- asymmetric viologen
- asymmetric
- novel class
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims description 20
- 230000002441 reversible effect Effects 0.000 claims abstract description 13
- 230000000638 stimulation Effects 0.000 claims abstract description 6
- 230000002950 deficient Effects 0.000 claims abstract description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000004146 energy storage Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 5
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical group N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 2
- 150000004292 cyclic ethers Chemical group 0.000 claims description 2
- 230000000813 microbial effect Effects 0.000 claims description 2
- 238000006276 transfer reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000002468 redox effect Effects 0.000 claims 2
- 239000003112 inhibitor Substances 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 14
- 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
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 238000010189 synthetic 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 20
- 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 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 229940125898 compound 5 Drugs 0.000 description 7
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- 238000005406 washing 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
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 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
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- -1 terpyridine compound Chemical class 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- 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 3
- 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
- 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
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229940125773 compound 10 Drugs 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 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
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-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
- 230000015572 biosynthetic process Effects 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
- 238000010586 diagram Methods 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
- 150000004820 halides Chemical class 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
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 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 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
- 150000005839 radical cations Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 2
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 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
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 238000013101 initial test Methods 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
- 238000005259 measurement Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 125000001424 substituent group Chemical group 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
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- 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
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- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- 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
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- 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
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Abstract
The invention discloses a novel asymmetric viologen compound which consists of acceptor 4,4' -bipyridine, different donor groups and different counter anions and has a structural formula
The invention also disclosesA synthetic method of a symmetrical viologen compound mainly combines different electron-rich donor groups with electron-deficient viologen dications, and then changes different counter anions to obtain a class of asymmetrical viologen compounds with different counter anions; the viologen compound has relatively stable electrochromic performance, and under the condition of electric stimulation, the viologen compound is accompanied with abundant color change because of reversible oxidation-reduction reaction, so that an electrochromic device which is driven by low voltage and has abundant 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 and a preparation method and application thereof.
Background
Materials that tend to reversibly change color under electrochemical stimulation are called electrochromic materials, a phenomenon known as Electrochromism (EC). These materials have been widely used in an electrochromic device (ECD) of an anti-glare rear view mirror or a low power display. Electrochromic (EC) materials can be broadly divided into two broad categories, namely inorganic materials and organic materials. Inorganic materials include transition metals and metal oxides, prussian blue series, lanthanide complexes, and the like. The organic material comprises viologen derivatives (1,1 '-dialkyl-4, 4' -bipyridinium), TTF (tetrathiafulvalene) derivatives, TCNQ (tetracyanoquinodimethane) derivatives, quinones, and conductive polymers, wherein the conductive polymers comprise polythiophene (PTh), Polyaniline (PANI), and polypyrrole (PPy). The most important characteristic of these materials is that they can exhibit a color change between the oxidized/reduced states under low voltage driving. Furthermore, the chemical structure design of EC materials plays a crucial role in determining their light absorption capabilities at different wavelengths, making them good candidates for low power applications.
Among these classes of materials, organic electrochromic materials are widely favored for their good optical properties, rich color, fast color conversion, good cyclic reversibility, easily modifiable structure, and low cost. Wherein the chemical structure of the organic micromolecule viologen is easy to modify, the redox state is rich, and the viologen has good redox reversibility and excellent electron accepting capability. Therefore, the material is also widely applied to the application fields of energy-saving intelligent windows, energy storage equipment and the like. However, the electron-withdrawing groups are introduced into the viologen, so that the electron-deficiency property of the viologen is enhanced and the dynamic stability of the electrochromic device is reduced. Therefore, different electron-rich donor groups are required to be introduced into the viologen, and the stability of the structure of the viologen compound is enhanced by utilizing the electron transfer between an electron donor unit and an electron acceptor unit; the viologen compound can be used as an electrochromic active material to develop an electrochromic device with large area and rich and variable colors, and further can realize the application of the viologen compound in an intelligent window.
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 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 purpose, the invention adopts the following technical scheme:
the novel asymmetric viologen compound is prepared by introducing a terpyridine compound onto 4,4 '-bipyridyl and then carrying out ion exchange to obtain viologen compounds with different counter anions, and a similar D-A structure is formed by utilizing the electron-rich characteristic of donor terpyridine and the electron-deficient characteristic of acceptor 4,4' -bipyridyl to enhance the stability of the viologen compound, and the novel asymmetric viologen compound has good reversible oxidation-reduction property; under the action of electrical stimulation, the novel asymmetric viologen compound generates reversible redox reaction and changes color, and is used as an active material and doped with proper electrolyte to prepare an electrochromic device with obvious color change. By optimizing the device, a large-area electrochromic device with rich color change and good cycle stability under low voltage can be manufactured, and the application of the device in an intelligent window is further realized.
The invention discloses a novel asymmetric viologen compoundThe agent is Tpy-Vio-X-The general structural formula is as follows:
wherein the content of the first and second substances,
X1 -is I-、Cl-、TFSI-、PF6 -、Br-、ClO4 -Or BF4 -Any one of the above;
X2 -is I-、Cl-、TFSI-、PF6 -、Br-、ClO4 -Or BF4 -Any one of the above;
n is 0 or 1;
r may be independently selected from a branched, straight, cyclic ether chain or cyclic alkyl chain having a positive integer of carbon atoms.
The synthetic route of the novel asymmetric viologen compound is divided into a route of two different products, namely n-0 and n-1, when n is 0, the product of the novel asymmetric viologen compound is marked as Tpy-Vio-1-X-(ii) a When n is 1, the product of the novel asymmetric viologen compound is labeled 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 X1And X2：
The novel asymmetric viologen compound comprises the following specific synthetic steps:
(1) preparation of compound 5: refluxing 4,4' -bipyridine and 1-chloro-2, 4-dinitrobenzene in acetonitrile, ethanol or acetone solvent for reaction for less than 72h, cooling to room temperature, filtering, spin-drying the filtrate, washing with acetone for 2 times, then washing with diethyl ether for 2 times, and then vacuum-drying to obtain a compound 5;
(2) preparation of compound 3: dissolving the compound 1 in methanol, adding the compound 2, adding a corresponding 15% potassium hydroxide aqueous solution, adding corresponding ammonia water, and stirring at 10-30 ℃ for less than 3 days; filtering to obtain filter cake, washing with alcohol and deionized water for 3 times, dissolving the filter cake with dichloromethane completely, extracting with saturated aqueous solution of sodium bicarbonate, concentrating until dichloromethane is dissolved, and adding large amount of methanol or ethanol for settling. 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: refluxing and stirring a compound 3, namely 10% palladium carbon by mass and 10mL of hydrazine hydrate in ethanol for 24 hours; cooling to room temperature, filtering to remove palladium carbon, and removing the solvent by rotary evaporation to obtain a compound 4;
(4) preparation of compound 6: carrying out reflux reaction on 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 precipitate to obtain a compound 6;
(5) compound Tpy-Vio-1-X-The preparation of (1): reacting the compound 6 with a halide in solvents such as DMSO, acetonitrile, DMF and alcohol at 30-45 ℃ for 12-24 hours in a nitrogen atmosphere respectively; 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 at room temperature for 5-24 hours; after the reaction is finished, filtering and recrystallizing to obtain a compound Tpy-Vio-1-X-；
(6) Preparation of compound 9: tetrakis (triphenylphosphine) palladium is used as a catalyst, the compound 7 and the compound 8 are dissolved in a 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 by anhydrous sodium sulfate, and removing the solvent by rotary evaporation to obtain a compound 9;
(7) preparation of compound 10: refluxing and stirring 9, 10mL of hydrazine hydrate, 10% by mass of palladium-carbon in ethanol for 24 h; cooling to room temperature, filtering to remove palladium carbon, and removing the solvent by rotary evaporation to obtain a compound 10;
(8) preparation of compound 11: carrying out reflux reaction on 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 precipitate to obtain a compound 11;
(9) compound Tpy-Vio-2-X-The preparation of (1): reacting the compound 11 with a halide in solvents such as DMSO, acetonitrile, DMF and alcohol at 30-45 ℃ for 12-24 hours in a nitrogen atmosphere respectively; 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 at room temperature for 5-24 hours; after the reaction is finished, filtering and recrystallizing to obtain a compound Tpy-Vio-2-X-。
The novel asymmetric viologen compound Tpy-Vio-1-X-Or Tpy-Vio-2-X-For an electro-active material, an electrochromic solution is prepared by doping a suitable electrolyte (imidazolium 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 pleochroic property and the multifunctional property are further realized.
The novel asymmetric viologen compound can be prepared into a material with electrochromism and electrochromism luminescence after being coupled with metal by introducing the metal, so as to obtain a bifunctional device.
The novel asymmetric viologen compound can be used as a color indicator, is connected with an energy storage device, and can be used for directly observing the charge and discharge states of the energy storage device.
The novel asymmetric viologen compound can be used for preparing an organic flow battery by utilizing the electron deficiency characteristic and the reversible redox characteristic of the novel asymmetric viologen compound.
The novel asymmetric viologen compound provided by the invention is used as a super capacitor by utilizing the easily-accepted electronic characteristic 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 in the asymmetric viologen compound.
The novel asymmetric viologen compounds of the present invention can be used to inhibit corrosion by microbial influences by modifying metals by coupling the metals with the terpyridine moiety of the asymmetric viologen compounds.
The novel asymmetric viologen compound can utilize ideal electron accepting capability and good oxidation-reduction behavior of viologen, thereby being used as an energy storage device.
The invention has the beneficial effects that: introducing a terpyridine compound onto 4,4' -bipyridine, and then carrying out ion exchange to obtain a novel asymmetric viologen compound with different counter anions, wherein the novel asymmetric viologen compound has excellent electrochemical and photophysical properties, and the electrochromic device is prepared by taking the novel asymmetric viologen compound as an electroactive material and doping a proper electrolyte; under the action of electrical stimulation, redox reversible reaction occurs, and the color of the device is obviously and abundantly changed. The novel asymmetric viologen compound related by the invention has simple synthesis steps and a plurality of oxidation reduction states, and can realize color change by applying low voltage. By optimizing the device, a large-area electrochromic device with rich color change and good circulation stability can be manufactured, and the application of the device in an intelligent window is further realized.
Drawings
FIG. 1a shows Tpy-Vio-1-X from example 2-(X1＝Cl,X2Negative oxidation peak of cyclic voltammogram (I);
FIG. 1b shows Tpy-Vio-1-X from example 2-(X1＝Cl,X2Positive oxidation peak of cyclic voltammogram of I);
FIG. 2 shows the use of Tpy-Vio-1-X in example 3-(X1＝Cl,X2I) making an electrochromic diagram of the device at an operating voltage;
FIG. 3a shows the use of Tpy-Vio-1-X in example 4-(X1＝Cl,X2I) absorption spectrum of the fabricated device under applied negative pressure;
FIG. 3b shows the use of Tpy-Vio-1-X in example 4-(X1＝Cl,X2I) absorption spectrum of the voltage after a period of continuous application;
FIG. 4 shows the use of Tpy-Vio-1-X in example 5-(X1＝Cl,X2I) transmittance change plot of the fabricated device under applied negative pressure;
FIG. 5 shows the use of Tpy-Vio-1-X in example 6-(X1＝Cl,X2I) current consumption diagram of the fabricated device under applied negative voltage;
FIG. 6 shows the use of Tpy-Vio-1-X in example 7-(X1＝Cl,X2I) devices made were tested for cycling stability under applied negative pressure.
Detailed Description
The following is a detailed description of the embodiments of the present invention, which is implemented on the premise of the technical solution of the present invention, and detailed implementation manners and specific operation procedures are given, but the scope 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, sensitive response to low voltage, similar synthesis steps and similar photophysical characteristics, and is denoted by Tpy-Vio-1-X-(X1＝Cl,X2The following is a detailed description of the example.
Example 1: Tpy-Vio-1-X-(X1＝Cl,X2Preparation of ═ I)
(1) Preparation of compound 5: 1-chloro-2, 4-dinitrobenzene (300mg,1.49mmol) and 4,4' -bipyridine (348mg,2.20mmol) are reacted in anhydrous acetonitrile under reflux for 48h, after the reaction is finished, the reaction solution is cooled to room temperature, filtered, the filtrate is dried by spinning and washed with acetone and diethyl ether for 3 times, and then filtered and dried in vacuum to obtain a compound 5. Yield: 70 percent.
1H NMR(400MHz,D2O)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: after completely dissolving compound 1(500mg,3.31mmol) in methanol, compound 2(800mg,6.62mmol) was added, 15mL of 15% KOH in water was added, and 15mL of aqueous ammonia was added and stirred at 25 ℃ for 3 days; after the reaction is finished, a large amount of black solid appears, the precipitate is collected by vacuum filtration, methanol and water are used for washing for 3 times respectively, then dichloromethane is used for dissolving the black solid, the black solid is transferred to a separating funnel, saturated sodium bicarbonate aqueous solution is added for washing for two times, an organic layer is transferred to a conical flask and dried by anhydrous sodium sulfate, the mixture is concentrated until the mixture is just dissolved, a large amount of methanol is added for standing and precipitating a large amount of precipitate, a filter cake is placed in a vacuum drying oven for drying for 12 hours after filtration, and the compound 3 is obtained by vacuum drying. Yield: 45 percent.
1H NMR(400MHz,CDCl3)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: refluxing and stirring a compound 3(400mg,1.10mmol), 10% by mass of palladium-carbon (80mg) and hydrazine hydrate (8mL) in ethanol for 24 h; cooling to room temperature, filtering to remove palladium carbon, removing solvent by rotary evaporation, adding water and dichloromethane for extraction, washing twice with saturated sodium chloride solution, drying with anhydrous sodium sulfate, and rotary drying to obtain compound 4. Yield: 90 percent.
1H NMR(400MHz,CDCl3)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: refluxing compound 4(324mg,0.43mmol) and compound 5(141mg,0.39mmol) in a mixed solvent of ethanol and deionized water for 84 h; cooling to room temperature, removing the solvent by rotary evaporation, adding a small amount of methanol to completely dissolve the solid, and then adding a large amount of acetone and ethyl acetate to precipitate to obtain a compound 6. Yield: 50 percent.
1H NMR(400MHz,DMSO-d6)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(0.5mmol,300mg) and iodomethane (8.0mmol,0.5mL) were reacted at 43 ℃ for 24h in an acetonitrile solvent and nitrogen atmosphere; after the reaction is finished, spin-drying the reaction solution, dissolving the reaction solution with DMSO (dimethyl sulfoxide), adding a proper amount of acetone, standing to separate out a precipitate, filtering, and vacuum-drying a filter cake to obtain a compound Tpy-Vio-1-X-(X1＝Cl,X2I). Yield: 60 percent.
1H NMR(400MHz,DMSO-d6)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)。
13C NMR(100MHz,DMSO-d6)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-(X1＝Cl,X2Cyclic voltammetry test of ═ I)
Tpy-Vio-1-X-(X1＝Cl,X2I) cyclic voltammetry test adopts 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/AgNO3. Tetrabutylammonium hexafluorophosphate in DMF (0.1M) was used as the electrolyte. The scanning speed was 100 mV. s-1。
Tpy-Vio-1-X-(X1＝Cl,X2I) is shown in fig. 1. As can be seen from FIG. 1a, the compound has three pairs of reversible redox peaks in the negative level, wherein two pairs of reversible redox peaks at the negative potential low potential correspond to the reduction potentials of one electron and two electrons of the viologen dication,a pair of reversible redox peaks near the high potential is generated corresponding to the electron gain and loss of nitrogen atoms on the terpyridine, and as can be seen from fig. 1b, the oxidation peak of the compound anode corresponds to the oxidation potential that iodide ions lose one electron, lose two electrons and lose three electrons.
Example 3: with Tpy-Vio-1-X-(X1＝Cl,X2I) color change of the resulting device under electrical stimulation
Tpy-Vio-1-X-(X1＝Cl,X2I) cyclic voltammogram of the device is shown in fig. 2. As can be seen from the figure, the compound is used as an electroactive material and is doped with a suitable electrolyte to prepare an electrochromic device, the electrochromic device shows orange color when no voltage is applied, and a preliminary voltage V is applied1＝after-1.2V, the color of the device changed to yellow-green, and the voltage V was continued to be applied2＝After-1.8 v, the color of the device changed to greenish black.
Example 4: with Tpy-Vio-1-X-(X1＝Cl,X2I) absorption spectroscopy of the resulting devices under applied operating voltage
The ultraviolet-visible spectrophotometer is used together with an electrochemical analyzer, wherein 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.
With Tpy-Vio-1-X-(X1＝Cl,X2Devices made of I) under application of a lower voltage V1When the optical characteristics of the device are changed, as can be seen from fig. 3a, a more obvious absorption peak appears at 721nm compared with 0V, and at this time, an electron obtained from the dicationic state should be converted into the radical cation state; continued application of voltage V2When the absorption peak at 556nm is blue-shifted by 35nm, the state of free radical cation should be changed into neutral state. As can be seen from fig. 3b, the absorption intensity does not increase any more after the voltage is continuously applied for a certain period of time, and the voltage is relatively stable.
Example 5: with Tpy-Vio-1-X-(X1＝Cl,X2Transmittance test of devices produced under applied operating voltage ═ I)
The measurement of the change of the transmittance of the device under different voltages requires the simultaneous use of an ultraviolet-visible spectrophotometer and an electrochemical analyzer.
With Tpy-Vio-1-X-(X1＝Cl,X2I) the absorption spectrum of the resulting device under the applied operating voltage is shown in fig. 4. As can be seen, when a lower voltage V is applied1At 679nm, the maximum transmittance is 31%, in this case for Tpy-Vio-1-X-(X1＝Cl,X2I) a radical cation state with one electron; continuously increasing the voltage V2At 679nm, the maximum transmittance is 60%, in this case for Tpy-Vio-1-X-(X1＝Cl,X2I) neutral states of two electrons.
Example 6: with Tpy-Vio-1-X-(X1＝Cl,X2I) current consumption test and cycling stability test of the produced component under the applied operating voltage
With Tpy-Vio-1-X-(X1＝Cl,X2I) the current consumption test of the fabricated device under the applied operating voltage is shown in fig. 5. With Tpy-Vio-1-X-(X1＝Cl,X2I) the device produced is tested for cycling stability under applied operating voltage as 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 when the operating voltage was applied, it was completely colored and the transmittance became 35%; after 4 hours of the coloring cycle, the transmittance can reach 90% when coloring and 40% when fading; the transmission at tinting was reduced by 0.6% compared to the initial test data. The device has the advantages that the coloring time is 10s, the fading time is 9s and the coloring efficiency is 95% under the working voltage; therefore, the device has better cycling stability.
Claims (10)
1. A novel asymmetric viologen compound is characterized in that the chemical structural formula is as follows:
wherein the content of the first and second substances,
X1 -is I-、Cl-、TFSI-、PF6 -、Br-、ClO4 -Or BF4 -Any one of the above;
X2 -is I-、Cl-、TFSI-、PF6 -、Br-、ClO4 -Or BF4 -Any one of the above;
r is independently selected from a branched, straight, cyclic ether chain or cyclic alkyl chain having a positive integer of carbon atoms.
2. The novel class of asymmetric viologen compounds of claim 1 having the chemical formula:
3. the process for preparing a novel class of asymmetric viologen compounds of claim 1 wherein when n is 0, the synthetic route for said compounds is as follows, wherein X comprises X1And X2：
4. The process for preparing a novel class of asymmetric viologen compounds of claim 1 wherein when n is 1, the synthetic route for said compounds is as follows, wherein X comprises X1And X2：
5. The use of a novel class of asymmetric viologen compounds as claimed in any of claims 1 to 2 for the preparation of electrochromic devices by their reversible redox properties under electrical stimulation.
6. The use of a novel class of asymmetric viologen compounds as claimed in any of claims 1 to 2, which can be used as a means of making organic flow batteries by their electron deficient and reversible redox properties.
7. Use of a novel class of asymmetric viologen compounds according to any of claims 1 to 2 as supercapacitors, taking advantage of the readily acceptable electronic properties of the asymmetric viologen compounds.
8. Use of a novel class of asymmetric viologen compounds according to any of claims 1 to 2, as electron transfer catalysts, wherein reversible electron transfer reactions can take place using the interior of the asymmetric viologen compound.
9. Use of a novel class of asymmetric viologen compounds according to any of claims 1 to 2, wherein metals are modified by coupling them to the terpyridine moiety of the asymmetric viologen compound to be used as corrosion inhibitors against microbial influences.
10. Use of a novel class of asymmetric viologen compounds according to any of claims 1 to 2 for use as energy storage devices, taking advantage of the ideal electron accepting ability and good redox behavior of viologens.
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