CN111807992A - 一类d-a型四氰基蒽醌二甲烷光电功能材料及其制备方法和应用 - Google Patents
一类d-a型四氰基蒽醌二甲烷光电功能材料及其制备方法和应用 Download PDFInfo
- Publication number
- CN111807992A CN111807992A CN202010581712.2A CN202010581712A CN111807992A CN 111807992 A CN111807992 A CN 111807992A CN 202010581712 A CN202010581712 A CN 202010581712A CN 111807992 A CN111807992 A CN 111807992A
- Authority
- CN
- China
- Prior art keywords
- compound
- formula
- hydrocarbon group
- aliphatic hydrocarbyl
- reaction
- 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.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 title abstract description 33
- 150000001875 compounds Chemical class 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000010410 layer Substances 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 17
- 238000010992 reflux Methods 0.000 claims description 17
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229960001701 chloroform Drugs 0.000 claims description 12
- 239000011368 organic material Substances 0.000 claims description 12
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- -1 nitro, hydroxy Chemical group 0.000 claims description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 7
- 229930192474 thiophene Natural products 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 6
- 239000012044 organic layer Substances 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000006708 (C5-C14) heteroaryl group Chemical group 0.000 claims description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 2
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229960003750 ethyl chloride Drugs 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- 238000000862 absorption spectrum Methods 0.000 abstract description 8
- 238000001228 spectrum Methods 0.000 abstract description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 38
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 229940076442 9,10-anthraquinone Drugs 0.000 description 17
- 239000007787 solid Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 239000008188 pellet Substances 0.000 description 12
- 238000000967 suction filtration Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 239000012065 filter cake Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 229920000144 PEDOT:PSS Polymers 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000005504 styryl group Chemical group 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- FCETXLHFBYOVCV-UHFFFAOYSA-N 2-(bromomethyl)anthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CBr)=CC=C3C(=O)C2=C1 FCETXLHFBYOVCV-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 125000005605 benzo group Chemical group 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 229940117389 dichlorobenzene Drugs 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 description 3
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- DQXKOHDUMJLXKH-PHEQNACWSA-N (e)-n-[2-[2-[[(e)-oct-2-enoyl]amino]ethyldisulfanyl]ethyl]oct-2-enamide Chemical compound CCCCC\C=C\C(=O)NCCSSCCNC(=O)\C=C\CCCCC DQXKOHDUMJLXKH-PHEQNACWSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- 125000006021 1-methyl-2-propenyl group Chemical group 0.000 description 1
- 125000006018 1-methyl-ethenyl group Chemical group 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 description 1
- 125000006022 2-methyl-2-propenyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- GWXUVWKBVROFDM-UHFFFAOYSA-N 4-hexoxybenzaldehyde Chemical compound CCCCCCOC1=CC=C(C=O)C=C1 GWXUVWKBVROFDM-UHFFFAOYSA-N 0.000 description 1
- VWCAHBARARIQLV-UHFFFAOYSA-N 5-hexylthiophene-2-carbaldehyde Chemical compound CCCCCCC1=CC=C(C=O)S1 VWCAHBARARIQLV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000004931 azocinyl group Chemical group N1=C(C=CC=CC=C1)* 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000004603 benzisoxazolyl group Chemical group O1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005046 dihydronaphthyl group Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000002467 indacenes Chemical class 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000003406 indolizinyl group Chemical group C=1(C=CN2C=CC=CC12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- 125000005329 tetralinyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/37—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by etherified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
- C07D207/327—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术领域
本发明属于有机材料领域,具体涉及一类D-A型四氰基蒽醌二甲烷衍生物光电功能材料及其制备方法以及应用。
背景技术
在能源问题日见突出的今天,如何制造出低成本、高效率的太阳电池成为许多科研者面临的共性关键技术难题。有机太阳电池(OSCs)因其有机体系的巨大多样性,以及原料成本低、制备成本低、能耗低、能够与柔性衬底兼容等优势,成为近年来人们研究的热点。经过科研工作者的努力,在短短二十来年的时间里,其光电转换效率(PCE)从10-2-10-3%提高到了17.27%[An Q,Ma X,Gao J,et al.Science Bulletin,2019,64(8):504-506]。采用有机小分子引达省衍生物为受体材料,以吸收互补、能级匹配的聚合物或小分子为给体材料,制备的OSCs的PCE不断被刷新,但是由于这类有机小分子受体材料的合成条件比较苛刻,合成收率较低,合成成本偏高,是商业化应用的瓶颈,因此探索和开发合成条件简单、收率高、性能优良、窄带隙的有机小分子受体材料来提高OSCs的PCE,简化合成条件、降低生产成本,将是OSCs商业化的必经之路。
四氰基蒽醌二甲烷具有良好的光化学和光物理稳定性以及很强的电子亲和势,自1985年作为受体材料研究以来[Kini,A.M.,et al.,Journal of the American ChemicalSociety,1985,107(3):556-562],引起人们的关注,但是该化合物溶解性差[Gautrot,J.E.,et al.,New Journal of Chemistry,2007.31(9):1585-1593],吸收光谱比较窄,具有很强的聚集诱导发光性,因而在有机太阳电池领域的应用受到限制。
发明内容
本发明提供了一种结构新颖的D-A型四氰基蒽醌二甲烷类小分子受体材料,该类材料具有良好的吸收光谱,优良的溶解性能和电子传输性能等诸多优点。
本发明涉及一种具有式(I)结构的化合物:
其中,R为非取代或者任选被一个、两个或多个Rs取代的C6-14芳基、5-14元杂芳基;R1、R2相同或不同,彼此独立地选自卤素、硝基、羟基、氰基、C1-6脂肪烃基、C1-6脂肪烃基-O-、C1-6脂肪烃基-S-;R3、R4相同或不同,彼此独立地选自氢或C1-6脂肪烃基;Rs选自C1-20脂肪烃基、C1-20脂肪烃基-O-、C1-20脂肪烃基-S-、OH、SH;m、n独立地选自0-4的整数;t为1或2。
根据本发明的实施方案,R为非取代或者任选被一个、两个或多个Rs取代的苯基、吡咯、噻吩;R1、R2相同或不同,彼此独立地选自C1-3脂肪烃基、C1-3脂肪烃基-O-、C1-3脂肪烃基-S-;R3、R4相同或不同,彼此独立地选自氢或C1-3脂肪烃基;Rs选自C1-12脂肪烃基、C1-12脂肪烃基-O-、C1-12脂肪烃基-S-;m、n独立地选自0、1、2、3;t为1或2。
根据本发明的实施方案,R4选自C1-8脂肪烃基、C1-8脂肪烃基-O-、C1-8脂肪烃基-S-。
根据本发明优选的实施方案,所述R基团可选自如下结构:
根据本发明的实施方案,式(I)具有以下式(II)或式(III)所示的结构:
其中,R、R1、R2、R3、R4、m、n独立地具有上文所述的定义。
根据本发明的实施方案,式(I)具有以下式(IV)所示的结构:
其中,R具有上文所述的定义。
本发明还提供式(I)所示化合物的制备方法,包括以下步骤:
将式M所示化合物与丙二腈反应,得到式(I)所示化合物;
其中,R、R1、R2、R3、R4、m、n、t独立地具有上文所述的定义。
根据本发明的实施方案,所述反应在有机溶剂存在下进行,所述有机溶剂优选为卤代烷烃,例如卤代C1-3烷烃,例如二氯甲烷、三氯甲烷、四氯化碳、氯乙烷。
根据本发明的实施方案,所述反应优选在TiCl4和缚酸剂存在条件下进行,所述缚酸剂优选为无水吡啶或N-甲基吗啉。
根据本发明的实施方案,所述反应优选先加入式M化合物,随后加入混合溶液,加热回流反应6-24h;再加入混合溶液,继续加热回流6-24h;所述混合溶液为丙二腈、TiCl4、缚酸剂按照摩尔比1:(0.5-1.5):(1-3)进行混合的溶液,所述摩尔比进一步优选为1:(0.8-1.2):(1.5-2.5)或1:(0.9-1.1):(1.8-2.2)。
根据本发明的实施方案,所述反应包括后处理步骤,例如,反应完毕后,将反应混合液倒入冰水中淬灭,分液萃取,合并有机层,干燥、抽滤、浓缩后经柱层析纯化得到目标产物。
本发明还提供了式(I)所示化合物在太阳能电池器件中的用途。
优选地,所述式(I)所示化合物的定义如前述所定义。
优选地,所述电池为有机太阳能电池。
本发明还提供了一种有机太阳能电池器件,包括:第一电极、设置成面对所述第一电极的第二电极、以及设置在所述第一电极和所述第二电极之间并且包括光活性层的一个、两个或更多个有机材料层;其中所述有机材料层包含式(I)所示的化合物。
根据本发明,所述第一电极的厚度为30-60nm,例如40nm、50nm;
根据本发明,所述第二电极的厚度为60-100nm,例如70nm、80nm、90nm;
根据本发明,所述有机材料层的厚度为30-120nm,例如30-60nm、60-120nm。
根据本发明,所述有机材料层中包括式(I)所示结构与聚3-己基噻吩的混合层;所述有机材料层还可以进一步包括PEDOT:PPS[聚(3,4-二氧乙烷噻吩):聚(苯乙烯磺酸盐)]混合物。
根据本发明,所述包含式(I)所示结构的化合物的材料层可用作太阳能电池光敏层。
优选地,所述式(I)化合物的定义如前述所定义。
有益效果
(1)本发明化合物有良好且稳定的溶解性。在光电功能材料领域,解决溶解性问题的通用方法是引入长链烷烃,但在四氰基蒽醌二甲烷体系中使用这一方法并不能有效解决这一问题。本发明引入的特殊取代结构,使四氰基蒽醌二甲烷小分子受体材料在普通的有机溶剂中即能具有良好的溶解性,且在保存三个月之后,仍稳定保持该良好溶解性。此外,由于特定取代结构的引入,意外的获得更好的可见光吸收性能等,采用该材料制备的光伏器件的短路电流有较大幅度的提高。因而,本发明的化合物材料有利于光电器件的制备与优化修饰,适于在太阳能电池材料领域广泛应用。
(2)本发明的化合物通过特殊取代结构的引入,克服了四氰基蒽醌二甲烷分子的聚集诱导发光性。其在固体膜和有机溶剂中加水都没有荧光性能,是一类性能优良的有机太阳能电池受体材料。
(3)本发明化合物引入共轭给体单元结构,形成给体-受体形式的共轭小分子受体材料,有效增加了分子共轭体系,增加分子的吸收范围和强度,吸收光谱与太阳光谱匹配良好,具有较大的太阳能电池材料开发利用价值。
附图说明
图1为本发明D-A型四氰基蒽醌二甲烷光电功能材料的示例性合成反应式。
图2为本发明制备出的(E)-2-[4`-(己氧基)苯乙烯基]-11,11,12,12-四氰基-9,10-蒽醌二甲烷的核磁共振氢谱图。
图3为本发明制备出的(E)-2-[4`-(己氧基)苯乙烯基]-11,11,12,12-四氰基-9,10-蒽醌二甲烷的核磁共振碳谱图。
图4为本发明制备出的(E)-2-[5`-己基-2`-噻吩乙烯基]-11,11,12,12-四氰基-9,10-蒽醌二甲烷的核磁共振氢谱图。
图5为本发明制备出的(E)-2-[5`-己基-2`-噻吩乙烯基]-11,11,12,12-四氰基-9,10-蒽醌二甲烷的核磁共振碳谱图。
图6为有机太阳能电池器件的结构示意图。
其中,1为ITO玻璃;2为PEDOT:PSS[聚(3,4-二氧乙烷噻吩):聚(苯乙烯磺酸盐)];3为含D-A型四氰基蒽醌二甲烷类受体材料和P3HT[聚(3-己基噻吩)]的共混薄膜;4为LiF;5为Al电极。
术语定义
本发明所涉及的“脂肪烃基”包括饱和或不饱和,直链或具有支链的链状烃基,所述脂肪烃基的类型可选自烷基、烯基、炔基等,所述脂肪烃基的碳原子数通常为1-20,进一步的优选范围包括1-12、2-8、3-7、4-6等,具体可包括但不限于如下基团:甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、新戊基、正己基、乙烯基、1-丙烯基、2-丙烯基、1-甲基乙烯基、1-丁烯基、1-乙基乙烯基、1-甲基-2-丙烯基、2-丁烯基、3-丁烯基、2-甲基-1-丙烯基、2-甲基-2-丙烯基、1-戊烯基、1-己烯基、乙炔基,1-丙炔基,2-丙炔基,1-丁炔基,1-甲基-2-丙炔基,3-丁炔基,1-戊炔基和1-己炔基;其他基团(例如脂肪烃基-O-)中所含“脂肪烃基”部分同上述解释。
术语“C6-10芳基”应理解为优选表示具有6、7、8、9、10、11、12、13或14个碳原子的一价芳香性或部分芳香性的单环、双环或三环烃环(“C6-14芳基”),特别是具有6个碳原子的环(“C6芳基”),例如苯基;或联苯基,或者是具有9个碳原子的环(“C9芳基”),例如茚满基或茚基,或者是具有10个碳原子的环(“C10芳基”),例如四氢化萘基、二氢萘基或萘基,或者是具有13个碳原子的环(“C13芳基”),例如芴基,或者是具有14个碳原子的环(“C14芳基”),例如蒽基。当所述C6-14芳基被取代时,其可以为单取代或者多取代。并且,对其取代位点没有限制,例如可以为邻位、对位或间位取代。
术语“5-14元杂芳基”应理解为具有5、6、7、8、9、10、11、12、13或14个环原子—特别是5或6或9或10个碳原子—且其包含1-5个—优选1-3个—独立选自N、O和S的杂原子的一价单环、双环或三环芳族环基团,并且,另外在每一种情况下可为苯并稠合的。特别地,杂芳基选自噻吩基、呋喃基、吡咯基、噁唑基、噻唑基、咪唑基、吡唑基、异噁唑基、异噻唑基、噁二唑基、三唑基、噻二唑基等以及它们的苯并衍生物,例如苯并呋喃基、苯并噻吩基、苯并噁唑基、苯并异噁唑基、苯并咪唑基、苯并三唑基、吲唑基、吲哚基、异吲哚基等;或吡啶基、哒嗪基、嘧啶基、吡嗪基、三嗪基等,以及它们的苯并衍生物,例如喹啉基、喹唑啉基、异喹啉基等;或吖辛因基、吲嗪基、嘌呤基等以及它们的苯并衍生物;或噌啉基、酞嗪基、喹唑啉基、喹喔啉基、萘啶基、蝶啶基、咔唑基、吖啶基、吩嗪基、吩噻嗪基、吩噁嗪基等。
术语“卤素”表示氟、氯、溴、碘。
具体实施方式
下文将结合具体实施例对本发明的制备方法做更进一步的详细说明。应当理解,下列实施例仅为示例性地说明和解释本发明,而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。下述实施例中所使用的实验方法如无特殊说明,均为常规方法;下述实施例中所用的试剂、材料等,如无特殊说明,均可从商业途径得到。
实施例1
化合物I-1:(E)-2-[4`-(己氧基)苯乙烯基]-11,11,12,12-四氰基-9,10-蒽醌二甲烷的合成
1.1 2-溴甲基-9,10-蒽醌的合成
将44.45克(0.2mol)的2-甲基-9,10-蒽醌、35.6克(0.2mol)的NBS、2.99克(12.3mmol)的过氧化苯甲酰和500mL的四氯化碳加入到1L的圆底烧瓶中,加热回流10个小时,自然冷却至室温后抽滤,滤饼用500mL的甲醇室温搅拌3个小时,抽滤后滤饼用600mL的乙酸乙酯重结晶得到淡黄色固体,65℃真空干燥10个小时得49.88克产品,收率为82.83%,熔点为198-199℃;IR(KBr压片,cm-1):3068.75,3032.1,2362.8,2343.51,1674.21,1589.34,1330.88,1323.17,1296.16,1228.66,981.77,931.62,879.54,860.25,794.67,727.16,711.73,675.09,634.58,615.29;1H NMR(400MHz,CDCl3)δ(ppm):8.32-8.35(m,4H),7.81-7.86(m,3H),4.61(s,2H)。
1.2 9,10-蒽醌-2-甲基溴化三苯基膦的合成
将24.1克(0.08mol)的2-溴甲基-9,10-蒽醌、24.1克(0.092mol)的三苯基膦和800mL的甲苯加入到1000mL的圆底烧瓶中,加热回流10个小时,自然冷却至室温后抽滤,滤饼用80mL的甲苯洗涤,65℃真空干燥10个小时得38.7克灰色固体粉末,收率为85.9%,熔点为315-316℃;IR(KBr压片,cm-1):3421.72,3053.32,3005.1,2872.01,2848.86,2773.64,1672.28,1593.2,1436.97,1325.1,1294.24,1112.93,997.2,931.62,860.25,850.61,746.45,715.59,707.88,690.52,542,513.07;1H NMR(400MHz,CDCl3)δ(ppm):8.17-8.19(m,2H),8.11-8.16(m,2H),8.03-8.09(m,6H),7.84-7.89(m,5H),7.73-7.81(m,6H),5.93-5.97(d,2H);13C NMR(CDCl3,100MHz,CDCl3)δ(ppm):182.21,181.89,138.12,138.07,135.19,135.16,134.83,.134.75,134.44,134.34,134.14,134.1,133.1,133.02,132.81,132.78,132.59,132.56,130.32,130.2,139.23,129.18,128.98,128.17,127.78,127.75,127.1,127.07,117.74,116.89.
1.3(E)-2-[4`-(己氧基)苯乙烯基]-9,10-蒽醌的合成
将16.9克(0.03mol)的2-[(三苯基溴化膦)-甲基]-9,10-蒽醌、6.26克(0.0303mol)的4-己氧基苯甲醛、5.04克(0.126mol)的氢化钠和300mL的四氢呋喃加入到500mL的圆底烧瓶中,氮气保护下加热回流12个小时,自然冷却至室温后抽滤,滤液中加入300mL的乙酸乙酯,用水洗涤3次,干燥过夜,旋蒸去溶剂,用50mL的甲醇重结晶,抽滤的黄色固体,用30mL的乙酸乙酯洗涤,通过采用正己烷:乙酸乙酯:氯仿=2:1:1为洗脱剂进行柱层析,65℃真空干燥10个小时得8.8克黄色固体粉末,收率为71.46%,熔点为114-115℃;IR(KBr压片,cm-1):2953.02,2933.73,2866.22,1670.35,1608.63,1589.34,1577.77,1512.19,1473.62,1327.03,1296.16,1265.3,1251.8,1178.51,1033.85,979.84,962.48,931.62,842.89,786.96,727.16,709.8,661.58,555.5;1H NMR(400MHz,CDCl3)δ(ppm):8.39(d,1H),8.31-8.34(m,2H),8.27-8.29(d,1H),7.86(d,1H),7.77-7.86(m,2H),7.5-7.53(t,2H),7.32-7.36(d,1H),7.06-7.1(d,1H),6.91-6.94(d,2H),3.98-4.01(t,2H),1.76-1.83(m,2H),1.44-1.54(m,2H),1.33-1.37(m,4H),0.9-0.93(m,3H);13C NMR(CDCl3,100MHz,CDCl3)δ(ppm):183.41,182.61,159.8,143.77,134.14,133.89,133.84,133.76,133.58,132.75,131.69,131.25,128.85,128.41,127.95,127.21,127.17,124.38,124.33,114.86,68.12,31.57,29.18,25.71,22.59,14.03.
1.4(E)-2-[4`-(己氧基)苯乙烯基]-11,11,12,12-四氰基-9,10-蒽醌二甲烷的合成
将3.69克(9mmol)的(E)-2-[4`-(己氧基)苯乙烯基]-9,10-蒽醌和无水三氯甲烷600mL加入到1L的三颈瓶中,搅拌下加入混合溶液A[丙二腈1.8克(27mmol)+TiCl4 5.4mL(49.3mmol)+无水吡啶4.5mL(55.86mmol)],加热回流反应18h后,再次加入A,回流24个小时后,自然冷却至室温后倒入冰水中淬灭反应,分液,水相用三氯甲烷(2×160mL)萃取,合并有机层,无水硫酸镁干燥过液,抽滤,浓缩后经柱层析(洗脱剂为二氯甲烷)纯化得紫黑色固体4.2克,收率92.1%;熔点为231-232℃;IR(KBr压片,cm-1):2951.09,2929.87,2858.51,2223.92,1625.99,1587.42,1556.55,1510.26,1469.76,1421.54,1330.88,1303.88,1286.52,1251.8,1224.8,1174.65,1122.57,1111,1026.13,962.48,904.61,835.18,769.6,694.37,667.37,634.58,597.93,565.14,518.85;1H NMR(400MHz,CDCl3)δ(ppm):8.23-8.32(m,4H),7.74-7.80(m,3H),7.51-7.53(m,2H),7.32(s,1H),7.01-7.05(d,1H),6.92-6.95(d,1H),4.01(t,2H),1.78-1.85(m,2H),1.45-1.52(m,2H),1.34-1.39(m,4H),0.93-0.95(t,3H);13C NMR(CDCl3,100MHz,CDCl3)δ(ppm):160.59,160.23,159.78,142.74,134.38,132.53,132.32,130.82,130.48,130.16,129.34,128.76,128.37,128.19,127.59,127.54,124.86,123.18,114.93,113.42,113.25,113.13,83.08,81.77,68.19,31.59,29.18,25.71,22.62,14.06.
实施例2
化合物I-2:(E)-2-[N-(2-乙基己基)-2`-吡咯乙烯基]-11,11,12,12-四氰基-9,10-蒽醌二甲烷的合成
2.1 2-溴甲基-9,10-蒽醌的合成
将44.45克(0.2mol)的2-甲基-9,10-蒽醌、35.6克(0.2mol)的NBS、2.99克(12.3mmol)的过氧化苯甲酰和500mL的四氯化碳加入到1L的圆底烧瓶中,加热回流10个小时,自然冷却至室温后抽滤,滤饼用500mL的甲醇室温搅拌3个小时,抽滤后滤饼用600mL的乙酸乙酯重结晶得到淡黄色固体,65℃真空干燥10个小时得49.88克产品,收率为82.83%,熔点为198-199℃;IR(KBr压片,cm-1):3068.75,3032.1,2362.8,2343.51,1674.21,1589.34,1330.88,1323.17,1296.16,1228.66,981.77,931.62,879.54,860.25,794.67,727.16,711.73,675.09,634.58,615.29;1H NMR(400MHz,CDCl3)δ(ppm):8.32-8.35(m,4H),7.81-7.86(m,3H),4.61(s,2H)。
2.2 9,10-蒽醌-2-甲基溴化三苯基膦的合成
将24.1克(0.08mol)的2-溴甲基-9,10-蒽醌、24.1克(0.092mol)的三苯基膦和800mL的甲苯加入到1000mL的圆底烧瓶中,加热回流10个小时,自然冷却至室温后抽滤,滤饼用80mL的甲苯洗涤,65℃真空干燥10个小时得38.7克灰色固体粉末,收率为85.9%,熔点为315-316℃;IR(KBr压片,cm-1):3421.72,3053.32,3005.1,2872.01,2848.86,2773.64,1672.28,1593.2,1436.97,1325.1,1294.24,1112.93,997.2,931.62,860.25,850.61,746.45,715.59,707.88,690.52,542,513.07;1H NMR(400MHz,CDCl3)δ(ppm):8.17-8.19(m,2H),8.11-8.16(m,2H),8.03-8.09(m,6H),7.84-7.89(m,5H),7.73-7.81(m,6H),5.93-5.97(d,2H);13C NMR(CDCl3,100MHz,CDCl3)δ(ppm):182.21,181.89,138.12,138.07,135.19,135.16,134.83,.134.75,134.44,134.34,134.14,134.1,133.1,133.02,132.81,132.78,132.59,132.56,130.32,130.2,139.23,129.18,128.98,128.17,127.78,127.75,127.1,127.07,117.74,116.89.
2.3(E)-2-[N-(2``-乙基己基)-2`-吡咯乙烯基]-9,10-蒽醌的合成
将11.26克(0.02mol)的2-[(三苯基溴化膦)-甲基]-9,10-蒽醌、4.19克(0.0202mol)的N-(2`-乙基己基)2-吡咯甲醛、5.6克(0.14mol)的氢化钠和600mL的四氢呋喃加入到1000mL的圆底烧瓶中,氮气保护下加热回流48个小时,自然冷却至室温后抽滤,滤液浓缩至300mL,加入300mL的乙酸乙酯,用水洗涤3次,有机相加入无水硫酸镁干燥过夜,滤除干燥剂、旋蒸去溶剂,用150mL的甲醇重结晶,抽滤的红色固体,用60mL的乙酸乙酯洗涤,所得深红色固体通过采用正己烷:乙酸乙酯:氯仿=2:1:1为洗脱剂进行柱层析,65℃真空干燥10个小时得5.87克深红色固体,收率为71.32%,熔点为65.7-68℃;IR(KBr压片,cm-1):2956.87,2927.94,2872.01,2858.51,1654.92,1585.49,1529.55,1475.54,1448.54,1328.95,1294.24,1076.28,979.84,950.91,931.62,779.24,705.95,665.44,638.44,611.43,542;1H NMR(400MHz,CDCl3)δ(ppm):8.30-8.32(t,3H),8.24-8.26(d,1H),7.75-7.80(m,3H),7.21-7.25(d,1H),6.94-6.98(d,1H),6.73(d,1H),6.64-6.65(d,1H),6.20-6.21(t,1H),3.89-3.92(t,2H),1.75-1.78(t,1H),1.27-1.37(m,8H),0.87-0.96(m,6H);13CNMR(CDCl3,100MHz,CDCl3)δ(ppm):183.40,182.48,144.12,134.11,133.88,133.82,133.58,131.28,130.73,130.65,127.99,127.16,124.87,123.88,123.04,121.22,108.80,108.48,50.93,41.41,30.61,28.66,23.97,23.02,14.05,10.76。
2.4(E)-2-[N-(2``-乙基己基)-2`-吡咯乙烯基]-11,11,12,12-四氰基-9,10-蒽醌二甲烷的合成
将8.23克(0.02mol)的(E)-2-[N-(2``-乙基己基)-2`-吡咯乙烯基]-9,10-蒽醌和无水三氯甲烷650mL加入到1L的三颈瓶中,搅拌下加入混合溶液A[丙二腈4克(60.5mmol)+TiCl4 12mL(60mmol)+无水吡啶10.3mL(120mmol)],加热回流反应18h后,再次加入A,回流24个小时后,自然冷却至室温后倒入冰水中淬灭反应,分液,水相用三氯甲烷(2×160mL)萃取,合并有机层,无水硫酸镁干燥过液,抽滤,浓缩后通过柱层析(洗脱剂为乙酸乙酯:三氯甲烷=1:1)分离得黑色固体7.75克,收率76.35%;熔点为238-240℃;IR(KBr压片,cm-1):2956.87,2927.94,28770.08,2362.8,2343.51,2223.92,1591.27,1558.48,1458.18,1325.1,1290.38,1174.65,931.62,769.6,711.73。
实施例3
化合物I-3:(E)-2-[5`-己基-2`-噻吩乙烯基]-11,11,12,12-四氰基-9,10-蒽醌二甲烷的合成
3.1 2-溴甲基-9,10-蒽醌的合成
将44.45克(0.2mol)的2-甲基-9,10-蒽醌、35.6克(0.2mol)的NBS、2.99克(12.3mmol)的过氧化苯甲酰和500mL的四氯化碳加入到1L的圆底烧瓶中,加热回流10个小时,自然冷却至室温后抽滤,滤饼用500mL的甲醇室温搅拌3个小时,抽滤后滤饼用600mL的乙酸乙酯重结晶得到淡黄色固体,65℃真空干燥10个小时得49.88克产品,收率为82.83%,熔点为198-199℃;IR(KBr压片,cm-1):3068.75,3032.1,2362.8,2343.51,1674.21,1589.34,1330.88,1323.17,1296.16,1228.66,981.77,931.62,879.54,860.25,794.67,727.16,711.73,675.09,634.58,615.29;1H NMR(400MHz,CDCl3)δ(ppm):8.32-8.35(m,4H),7.81-7.86(m,3H),4.61(s,2H)。
3.2 9,10-蒽醌-2-甲基溴化三苯基膦的合成
将24.1克(0.08mol)的2-溴甲基-9,10-蒽醌、24.1克(0.092mol)的三苯基膦和800mL的甲苯加入到1000mL的圆底烧瓶中,加热回流10个小时,自然冷却至室温后抽滤,滤饼用80mL的甲苯洗涤,65℃真空干燥10个小时得38.7克灰色固体粉末,收率为85.9%,熔点为315-316℃;IR(KBr压片,cm-1):3421.72,3053.32,3005.1,2872.01,2848.86,2773.64,1672.28,1593.2,1436.97,1325.1,1294.24,1112.93,997.2,931.62,860.25,850.61,746.45,715.59,707.88,690.52,542,513.07;1H NMR(400MHz,CDCl3)δ(ppm):8.17-8.19(m,2H),8.11-8.16(m,2H),8.03-8.09(m,6H),7.84-7.89(m,5H),7.73-7.81(m,6H),5.93-5.97(d,2H);13C NMR(CDCl3,100MHz,CDCl3)δ(ppm):182.21,181.89,138.12,138.07,135.19,135.16,134.83,.134.75,134.44,134.34,134.14,134.1,133.1,133.02,132.81,132.78,132.59,132.56,130.32,130.2,139.23,129.18,128.98,128.17,127.78,127.75,127.1,127.07,117.74,116.89。
3.3(E)-2-[5`-己基-2`-噻吩乙烯基]-9,10-蒽醌
将11.26克(0.02mol)的2-[(三苯基溴化膦)-甲基]-9,10-蒽醌、3.53克(0.018mol)的5-己基噻吩-2-甲醛、5.63克(0.141mol)的氢化钠和600mL的四氢呋喃加入到1000mL的圆底烧瓶中,氮气保护下加热回流18个小时,自然冷却至室温后倒入到500mL的冰水中,乙酸乙酯萃取(200mL×3次),合并有机相用饱和食盐水洗涤(100mL×2次),有机相加入无水硫酸镁干燥过夜,滤除干燥剂、旋蒸去溶剂,得到棕色固体,通过采用正己烷:乙酸乙酯:氯仿=20:1:1为洗脱剂进行柱层析,65℃真空干燥10个小时得5.93克橘红色固体,收率为82.25%,熔点为107.6-108.7℃;IR(KBr压片,cm-1):2954.95,2926.01,2852.72,2364.73,2341.58,1672.28,1622.13,1589.34,1564.27,1462.04,1325.1,1099.43,985.62,947.05,931.62,833.25,800.46,785.03,709.8,663.51,547.78;1H NMR(400MHz,CDCl3)δ(ppm):8.27-8.30(m,3H),8.21-8.23(d,1H),7.74-7.79(m,3H),7.38-7.42(d,1H),6.96-6.97(d,1H),6.82-6.86(d,1H),6.69-6.70(d,1H),2.78-2.82(t,2H),1.65-1.72(m,2H),1.31-1.40(m,6H),0.88-0.92(t,3H);13C NMR(CDCl3,100MHz,CDCl3)δ(ppm):183.23,182.44,147.60,143.25,139.47,134.08,133.82,133.79,133.71,133.51,131.64,131.04,128.38,127.91,127.16,127.12,126.41,124.98,124.68,124.16,31.54,31.42,30.46,28.74,22.55,14.06。
3.4(E)-2-[5`-己基-2`-噻吩乙烯基]-11,11,12,12-四氰基-9,10-蒽醌二甲烷的合成
将6克(0.015mol)的(E)-2-[5`-己基-2`-噻吩乙烯基]-9,10-蒽醌和无水三氯甲烷600mL加入到1L的三颈瓶中,搅拌下加入混合溶液A[丙二腈3克(45mmol)+TiCl4 9mL(45mmol)+无水吡啶7.5mL(90mmol)],加热回流反应12h后,再次加入A,回流24个小时后,自然冷却至室温后倒入冰水中淬灭反应,分液,水相用三氯甲烷(2×150mL)萃取,合并有机层,无水硫酸镁干燥过液,抽滤,浓缩后通过柱层析(洗脱剂为石油醚:三氯甲烷=1:1)分离得黑色固体7.1克,收率95.3%;熔点为194-195℃;IR(KBr压片,cm-1):2953.02,2926.01,2854.65,2223.92,1620.21,1597.06,1587.42,1556.55,1462.04,1328.95,1284.59,1211.3,1182.36,1122.57,1107.14,1037.7,950.91,902.69,823.6,798.53,769.6,694.37,671.23,599.86;1H NMR(400MHz,CDCl3)δ(ppm):8.18-8.26(m,4H),7.68-7.73(m,3H),7.36-7.40(d,1H),7.01-7.02(d,1H),6.79-6.83(d,1H),6.72-6.73(d,1H),2.79-2.83(t,2H),1.64-1.72(m,2H),1.29-1.39(m,6H),0.87-0.91(t,3H);13C NMR(CDCl3,100MHz,CDCl3)δ(ppm):160.49,159.65,148.55,142.21,138.98,132.48,132.27,130.80,130.41,130.08,129.35,129.14,128.14,127.84,127.52,127.49,125.20,124.57,123.46,113.39,113.36,113.18,113.06,83.04,81.68,31.50,31.40,30.49,28.69,22.52,14.04。
实施例4
参照实施例1、实施例2或实施例3的合成方法合成具体化合物结构,如下表:
表1
实施例5有机太阳能电池器件的制备
5mg化合物I-1与10mg P3HT[聚(3-己基噻吩)]混合,加入1mL二氯苯溶解,通过旋涂方式在经PEDOT:PSS修饰过的ITO玻璃基板上制备出薄膜,然后真空蒸镀LiF和Al制备出阴极。
该小分子受体材料的吸收光谱位于紫外可见及近红外区(200-800nm),器件性能为:白光1.5G(100mW/cm2)照射下,开路电压(Voc)=0.96V;短路电流(Isc)=3.52mA/cm2;填充因子(FF)=0.62。
实施例6有机太阳能电池器件的制备
5mg化合物I-2与10mg P3HT[聚(3-己基噻吩)]混合,加入1mL二氯苯溶解,通过旋涂方式在经PEDOT:PSS修饰过的ITO玻璃基板上制备出薄膜,然后真空蒸镀LiF和Al制备出阴极。
该小分子受体材料的吸收光谱位于紫外可见及近红外区(200-900nm),器件性能为:白光1.5G(100mW/cm2)照射下,开路电压(Voc)=0.98V;短路电流(Isc)=6.58mA/cm2;填充因子(FF)=0.71。
实施例7有机太阳能电池器件的制备
5mg化合物I-1与10mg P3HT[聚(3-己基噻吩)]混合,加入1mL二氯苯溶解,通过旋涂方式在经PEDOT:PSS修饰过的ITO玻璃基板上制备出薄膜,然后真空蒸镀LiF和Al制备出阴极。
该小分子受体材料的吸收光谱位于紫外可见及近红外区(200-880nm),器件性能为:白光1.5G(100mW/cm2)照射下,开路电压(Voc)=0.99V;短路电流(Isc)=8.26mA/cm2;填充因子(FF)=0.76。
实施例8有机太阳能电池器件的制备
按照上述方法替换化合物I-1为其他合成得到的化合物(化合物I-4~I-16)进行有机太阳能电池器件的制备。化合物I-4~I-16的吸收光谱位于紫外可见及近红外区(200-900nm),所得器件性能为:白光1.5G(100mW/cm2)照射下,开路电压(Voc)=0.9-1.2V;短路电流(Isc)=1.2-8.6mA/cm2;填充因子(FF)=0.5-0.8。
本发明太阳能电池器件结构如图6所示,1为ITO玻璃,2为PEDOT:PSS[聚(3,4-二氧乙烷噻吩):聚(苯乙烯磺酸盐)],其厚度为30-60nm,3为含四氰基蒽醌二甲烷衍生物I-1~I-16受体材料和P3HT[聚(3-己基噻吩)]的共混薄膜,其厚度为60-120nm,4为LiF,其厚度为,1-10nm,5为Al电极,其厚度为60-100nm。
实施例9本发明化合物溶解性实验
本发明的四氰基蒽醌二甲烷衍生物类受体材料(实施例制备的本发明化合物I-1至I-9)在常见溶剂中有良好的溶解性,且在保存三个月之后,在上述常见溶剂中仍有良好溶解性,具体参见表2实验数据。
表2
实施例10本发明化合物的光伏性能
本发明的D-A型四氰基蒽醌二甲烷类受体材料由于具有良好的溶解性,良好的可见光吸收性能,光伏器件的短路电流有较大幅度的提高,实现了预期的良好效果,具体参见表3实验数据,可见本发明的化合物相较于作为对比的其他四氰基蒽醌型化合物,光伏性能有明显提升。
表3
以上,对本发明的实施方式进行了说明。但是,本发明不限定于上述实施方式。凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
2.根据权利要求1所述化合物,其特征在于,R为非取代或者任选被一个、两个或多个Rs取代的苯基、吡咯、噻吩;R1、R2相同或不同,彼此独立地选自C1-3脂肪烃基、C1-3脂肪烃基-O-、C1-3脂肪烃基-S-;R3、R4相同或不同,彼此独立地选自氢或C1-3脂肪烃基;Rs选自C1-12脂肪烃基、C1-12脂肪烃基-O-、C1-12脂肪烃基-S-;m、n独立地选自0、1、2、3;t为1或2。
3.根据权利要求1或2所述化合物,其特征在于,R4选自C1-8脂肪烃基、C1-8脂肪烃基-O-、C1-8脂肪烃基-S-。
7.权利要求1所述化合物的制备方法,包括以下步骤:
将式M所示化合物与丙二腈反应,得到式(I)所示化合物;
其中,R、R1、R2、R3、R4、m、n、t独立地权利要求1-4任一项所述的定义;
优选地,所述反应在有机溶剂存在下进行,所述有机溶剂优选为卤代烷烃,例如卤代C1-3烷烃,例如二氯甲烷、三氯甲烷、四氯化碳、氯乙烷;
优选地,所述反应优选在TiCl4和缚酸剂存在条件下进行,所述缚酸剂优选为无水吡啶或N-甲基吗啉;
优选地,所述反应优选先加入式M化合物,随后加入混合溶液,加热回流反应6-24h;再加入混合溶液,继续加热回流6-24h;所述混合溶液为丙二腈、TiCl4、缚酸剂按照摩尔比1:(0.5-1.5):(1-3)进行混合的溶液,所述摩尔比进一步优选为1:(0.8-1.2):(1.5-2.5)或1:(0.9-1.1):(1.8-2.2);
优选地,所述反应包括后处理步骤,例如,反应完毕后,将反应混合液倒入冰水中淬灭,分液萃取,合并有机层,干燥、抽滤、浓缩后经柱层析纯化得到目标产物。
8.权利要求1-6任一项所述化合物在太阳能电池器件中的用途。
优选地,所述电池为有机太阳能电池。
9.一种有机太阳能电池器件,包括:第一电极、设置成面对所述第一电极的第二电极、以及设置在所述第一电极和所述第二电极之间并且包括光活性层的一个、两个或更多个有机材料层;所述有机材料层包含权利要求1-6任一项所述化合物;
优选地,所述第一电极的厚度为30-60nm;
优选地,所述第二电极的厚度为60-100nm;
优选地,所述有机材料层的厚度为30-120nm,例如30-60nm、60-120nm。
10.根据权利要求9所述有机太阳能电池器件,其特征在于,所述有机材料层中包括权利要求1-6任一项所述化合物与聚3-己基噻吩的混合层;
优选地,所述有机材料层还可以进一步包括PEDOT:PPS[聚(3,4-二氧乙烷噻吩):聚(苯乙烯磺酸盐)]混合物;
优选地,包含权利要求1-6任一项所述化合物的有机材料层可用作太阳能电池光敏层。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010581712.2A CN111807992B (zh) | 2020-06-23 | 2020-06-23 | 一类d-a型四氰基蒽醌二甲烷光电功能材料及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010581712.2A CN111807992B (zh) | 2020-06-23 | 2020-06-23 | 一类d-a型四氰基蒽醌二甲烷光电功能材料及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111807992A true CN111807992A (zh) | 2020-10-23 |
CN111807992B CN111807992B (zh) | 2023-12-05 |
Family
ID=72845934
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010581712.2A Active CN111807992B (zh) | 2020-06-23 | 2020-06-23 | 一类d-a型四氰基蒽醌二甲烷光电功能材料及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111807992B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115286534A (zh) * | 2022-04-26 | 2022-11-04 | 安徽工程大学 | 一种特异性检测Hg2+的近红外荧光化学传感器及其制备方法和应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102796245A (zh) * | 2011-05-25 | 2012-11-28 | 海洋王照明科技股份有限公司 | 含氰基蒽醌单元的共轭聚合物材料及其制备方法和应用 |
CN111087323A (zh) * | 2018-10-24 | 2020-05-01 | 河南省化工研究所有限责任公司 | 四氰基蒽醌二甲烷小分子受体材料及其制备方法和应用 |
-
2020
- 2020-06-23 CN CN202010581712.2A patent/CN111807992B/zh active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102796245A (zh) * | 2011-05-25 | 2012-11-28 | 海洋王照明科技股份有限公司 | 含氰基蒽醌单元的共轭聚合物材料及其制备方法和应用 |
CN111087323A (zh) * | 2018-10-24 | 2020-05-01 | 河南省化工研究所有限责任公司 | 四氰基蒽醌二甲烷小分子受体材料及其制备方法和应用 |
Non-Patent Citations (1)
Title |
---|
FILIP BURES 等: "New Push-Pull Chromophores Featuring TCAQ (11,11,12,12-Tetracyano-9,10-anthraquinodimethane) and Other Dicyanovinyl Acceptors" * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115286534A (zh) * | 2022-04-26 | 2022-11-04 | 安徽工程大学 | 一种特异性检测Hg2+的近红外荧光化学传感器及其制备方法和应用 |
CN115286534B (zh) * | 2022-04-26 | 2023-08-15 | 安徽工程大学 | 一种特异性检测Hg2+的近红外荧光化学传感器及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
CN111807992B (zh) | 2023-12-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109666033B (zh) | 基于九并稠杂环类共轭小分子及其制备方法与应用 | |
CN108864137B (zh) | 一种受体化合物、制备方法、用途以及含有其的光伏电池 | |
JP5425338B2 (ja) | アントラセンとピアセレノール類とを含有する共重合体、その製造方法及びその応用 | |
CN109232604A (zh) | 稠环非富勒烯受体材料及其制备方法、有机太阳能电池 | |
CN112608309B (zh) | 一种含芴环基团的非稠环有机小分子材料及其制备方法和应用 | |
CN112047958B (zh) | 一种含噻蒽端基的有机共轭小分子材料及其制备方法 | |
CN109517142B (zh) | 基于三茚并五元芳杂环的星型d-a结构共轭分子及其制备方法和应用 | |
CN109912621B (zh) | 一种不对称的萘核小分子受体材料及其制备方法和应用 | |
CN111807992B (zh) | 一类d-a型四氰基蒽醌二甲烷光电功能材料及其制备方法和应用 | |
CN110194778A (zh) | 一种多臂结构有机光伏材料及其制备方法与应用 | |
CN108192083B (zh) | 含三氟甲基的共轭聚合物及其制备方法和应用 | |
CN109265656A (zh) | 双烷硫链取代的共轭聚合物及其制备和应用 | |
CN112279856B (zh) | 一种非外围取代的可溶性金属酞菁及其合成方法和应用、一种钙钛矿太阳能电池 | |
CN110577548A (zh) | 基于二噻吩并吡咯的非对称稠杂环小分子电子受体材料及其应用 | |
CN109553625A (zh) | 一种马鞍型苝酰亚胺四聚体及其制备方法与应用 | |
CN112608333B (zh) | 基于双噻二唑咔唑衍生物小分子及其合成方法与在有机光电器件中的应用 | |
CN114316221A (zh) | 一类聚噻吩及其制备方法与应用 | |
CN109265468B (zh) | 含有反芳香性引达省并二噻吩单元的小分子及其在有机光伏中的应用 | |
CN114621251A (zh) | 基于喹喔啉衍生物的稠环单元、含该单元的小分子、聚合物及制备方法与应用 | |
CN109836369B (zh) | 一种螺茚类空穴传输小分子及其在钙钛矿太阳能电池的应用 | |
CN109810121B (zh) | 基于硫芴的稠环非富勒烯受体化合物、其制备方法及在太阳能电池中的应用 | |
CN110003245B (zh) | 一类烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭化合物及其制备方法与应用 | |
CN106832231A (zh) | 含1,2,3三唑并异吲哚‑5,7(2h,6h)‑二酮的共轭聚合物及其制法与应用 | |
CN111087323A (zh) | 四氰基蒽醌二甲烷小分子受体材料及其制备方法和应用 | |
CN113637023B (zh) | 一种不对称的吲哚衍生物核小分子受体材料及其制备方法 |
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 |