CN115124561A - Novel seven-membered ring-containing conjugated molecular material based on quinoid structure and preparation and application thereof - Google Patents
Novel seven-membered ring-containing conjugated molecular material based on quinoid structure and preparation and application thereof Download PDFInfo
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- CN115124561A CN115124561A CN202110333429.2A CN202110333429A CN115124561A CN 115124561 A CN115124561 A CN 115124561A CN 202110333429 A CN202110333429 A CN 202110333429A CN 115124561 A CN115124561 A CN 115124561A
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- aromatic hydrocarbon
- polycyclic aromatic
- membered ring
- compound
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- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 230000005669 field effect Effects 0.000 claims abstract description 30
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 230000005540 biological transmission Effects 0.000 claims abstract description 10
- 238000006722 reduction reaction Methods 0.000 claims abstract description 10
- 238000005698 Diels-Alder reaction Methods 0.000 claims abstract description 8
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 8
- 238000006482 condensation reaction Methods 0.000 claims abstract description 8
- 238000005935 nucleophilic addition reaction Methods 0.000 claims abstract description 8
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 52
- -1 phenyl diketone compound Chemical class 0.000 claims description 37
- 125000003118 aryl group Chemical group 0.000 claims description 28
- 125000001424 substituent group Chemical group 0.000 claims description 25
- 125000003545 alkoxy group Chemical group 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 21
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 21
- 125000001072 heteroaryl group Chemical group 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 6
- 239000007818 Grignard reagent Substances 0.000 claims description 5
- 230000004927 fusion Effects 0.000 claims description 5
- 150000004795 grignard reagents Chemical class 0.000 claims description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- 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 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 9
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
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- 239000003208 petroleum Substances 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 239000011698 potassium fluoride Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 3
- KLLLJCACIRKBDT-UHFFFAOYSA-N 2-phenyl-1H-indole Chemical compound N1C2=CC=CC=C2C=C1C1=CC=CC=C1 KLLLJCACIRKBDT-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000004639 Schlenk technique Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- 235000003270 potassium fluoride Nutrition 0.000 description 3
- HYXMHAHVUFTVFZ-UHFFFAOYSA-N (3-formylthiophen-2-yl)boronic acid Chemical compound OB(O)C=1SC=CC=1C=O HYXMHAHVUFTVFZ-UHFFFAOYSA-N 0.000 description 2
- 229920003026 Acene Polymers 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- SPXSEZMVRJLHQG-XMMPIXPASA-N [(2R)-1-[[4-[(3-phenylmethoxyphenoxy)methyl]phenyl]methyl]pyrrolidin-2-yl]methanol Chemical compound C(C1=CC=CC=C1)OC=1C=C(OCC2=CC=C(CN3[C@H](CCC3)CO)C=C2)C=CC=1 SPXSEZMVRJLHQG-XMMPIXPASA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 229940127271 compound 49 Drugs 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 150000002964 pentacenes Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical group CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000005406 washing Methods 0.000 description 2
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 1
- NPAXPTHCUCUHPT-UHFFFAOYSA-N 3,4,7,8-tetramethyl-1,10-phenanthroline Chemical compound CC1=CN=C2C3=NC=C(C)C(C)=C3C=CC2=C1C NPAXPTHCUCUHPT-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- JQUCWIWWWKZNCS-LESHARBVSA-N C(C1=CC=CC=C1)(=O)NC=1SC[C@H]2[C@@](N1)(CO[C@H](C2)C)C=2SC=C(N2)NC(=O)C2=NC=C(C=C2)OC(F)F Chemical compound C(C1=CC=CC=C1)(=O)NC=1SC[C@H]2[C@@](N1)(CO[C@H](C2)C)C=2SC=C(N2)NC(=O)C2=NC=C(C=C2)OC(F)F JQUCWIWWWKZNCS-LESHARBVSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- SMNRFWMNPDABKZ-WVALLCKVSA-N [[(2R,3S,4R,5S)-5-(2,6-dioxo-3H-pyridin-3-yl)-3,4-dihydroxyoxolan-2-yl]methoxy-hydroxyphosphoryl] [[[(2R,3S,4S,5R,6R)-4-fluoro-3,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-hydroxyphosphoryl]oxy-hydroxyphosphoryl] hydrogen phosphate Chemical compound OC[C@H]1O[C@H](OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)OC[C@H]2O[C@H]([C@H](O)[C@@H]2O)C2C=CC(=O)NC2=O)[C@H](O)[C@@H](F)[C@@H]1O SMNRFWMNPDABKZ-WVALLCKVSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WXMZPPIDLJRXNK-UHFFFAOYSA-N butyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CCCC)C1=CC=CC=C1 WXMZPPIDLJRXNK-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- CXQRZKIIGJLWPJ-UHFFFAOYSA-N diphenylphosphane;1-naphthalen-1-ylnaphthalene Chemical group C=1C=CC=CC=1PC1=CC=CC=C1.C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 CXQRZKIIGJLWPJ-UHFFFAOYSA-N 0.000 description 1
- CRHWEIDCXNDTMO-UHFFFAOYSA-N ditert-butylphosphane Chemical compound CC(C)(C)PC(C)(C)C CRHWEIDCXNDTMO-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- KZGWPHUWNWRTEP-UHFFFAOYSA-N ethynyl-tri(propan-2-yl)silane Chemical group CC(C)[Si](C#C)(C(C)C)C(C)C KZGWPHUWNWRTEP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
- B05D1/005—Spin coating
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Abstract
The invention discloses a novel conjugated molecular material containing seven-membered rings based on a quinoid structure, and a preparation method and application thereof. The structural formula of the novel conjugated molecular material is shown as follows. The synthesis of the novel conjugated compound containing the seven-membered ring based on the quinoid structure is successfully realized by five steps of Suzuki coupling reaction, condensation reaction, Diels-Alder reaction, nucleophilic addition reaction and reduction reaction from commercially available raw materials. Synthetic routeThe reactions involved are mostly relatively efficient. The novel conjugated compound containing seven-membered rings based on the quinoid structure is novel in structure, good in stability and good in solubility in common organic solvents. The novel conjugated compound containing seven-membered rings and designed and synthesized based on the quinoid structure has better transmission performance and solubility, and can be applied to the preparation of p-type field effect devices.
Description
Technical Field
The invention belongs to the field of organic material synthesis and material chemistry, and particularly relates to a novel seven-membered ring-containing conjugated molecular material based on a quinoid structure, and preparation and application thereof.
Background
The organic photoelectric functional material has the advantages of various types, adjustable structure, flexibility, light weight, large-area preparation and the like, so that the organic photoelectric functional material is widely concerned. The acene compound is an important organic functional material, the energy level of acene molecules is gradually changed along with the increase of the number of conjugated benzene rings, and the transition and transmission capability of electrons are greatly improved, so that the improvement of photoelectric function is facilitated. Pentacene compounds are star compounds, and the maximum hole mobility of the single crystal field effect device of the pentacene compounds can reach 35cm 2 Vs, in addition, is considered as a promising photoelectric conversion material due to its small molecular weight, simple structure, high yield of singlet fission, and having a diradical property.
Compared with other aromatic compounds, the quinoid structure has the following characteristics: 1) the band gap is narrow, red shift is absorbed, and the method has potential application in the fields of near infrared absorption and the like; 2) the molecules are tightly packed, the intermolecular force is strong, and the photoelectric function is promoted; 3) resonance isomerism of quinoid and Kaikuler structures exists, and potential biradical properties are possessed. Based on the characteristics, the quinoid conjugated molecule has huge development prospects in the fields of organic field effect transistors, near-infrared absorption, fluorescence, free-base materials, magnetic materials, organic thermoelectric materials and the like.
Disclosure of Invention
The invention aims to provide a seven-membered ring conjugated compound based on a quinoid structure and a preparation method and application thereof. The invention designs and develops a new seven-membered ring-containing novel conjugated molecule with a novel quinoid structure, synthesizes the conjugated molecule through five steps of reactions such as Suzuki coupling reaction, condensation reaction, Diels-Alder reaction, nucleophilic addition reaction, reduction reaction and the like, tests the basic photophysical characteristics and the performance of an organic field effect transistor of the molecular materials, and shows p-type transmission performance.
The seven-membered ring conjugated compound based on the quinoid structure provided by the invention has the structural formula shown as the formula I:
in the formula I, Ar refers to a polycyclic aromatic hydrocarbon structure, the polycyclic aromatic hydrocarbon structure at least contains one aromatic ring, the aromatic ring is independently selected from any one of aryl, heteroaryl, aryl containing substituent groups and heteroaryl containing substituent groups, and the bonding mode in the group is selected from at least one of single bond, double bond, triple bond and fusion;
the substituent in the aryl group containing a substituent and the heteroaryl group containing a substituent may be any one of a linear or branched alkyl group (specifically, methyl, t-butyl and hexyl) of C1 to C50, an alkoxy group (specifically, methoxy, t-butoxy and hexyloxy) of C1 to C50, an aralkyl group (specifically, t-butylphenyl and trimethylphenyl) of C6 to C50, and a heteroalkyl group (specifically, trimethylsilyl and triisopropylsilylethynyl) of C1 to C50;
specifically, Ar may be any one of the following 1 to 15:
in the structural formulas 1 to 15, R can be any one selected from H, C1-C50 straight-chain or branched-chain alkyl groups (specifically, methyl, tert-butyl and hexyl groups), C1-C50 alkoxy groups (specifically, methoxy, tert-butoxy and hexyloxy groups), C6-C50 aralkyl groups (specifically, tert-butylphenyl and trimethylphenyl groups), and C1-C50 heteroalkyl groups (specifically, trimethylsilyl and triisopropylsilylethynyl groups);
r on the seven-membered ring in the formula I is any one of linear or branched alkyl (specifically, methyl, tert-butyl and hexyl) of H, C1-C50, alkoxy (specifically, methoxy, tert-butoxy and hexyloxy) of C1-C50, aralkyl (specifically, tert-butylphenyl and trimethylphenyl) of C6-C50 and heteroalkyl (specifically, trimethylsilyl and triisopropylsilylethynyl) of C1-C50, specifically, triisopropylsilylethynyl;
specifically, the seven-membered ring-containing conjugated compound based on the quinoid structure shown in formula I is one of the following compounds 16 to 30:
r on the seven-membered ring in the formula I is any one of linear or branched alkyl groups (specifically, methyl, tert-butyl and hexyl) selected from H, C1-C50, alkoxy groups (specifically, methoxy, tert-butoxy and hexyloxy) selected from C1-C50, aralkyl groups (specifically, tert-butylphenyl and trimethylphenyl) selected from C6-C50 and heteroalkyl groups (specifically, trimethylsilyl and triisopropylsilylethynyl) selected from C1-C50, specifically, triisopropylsilylethynyl;
each of the other Rs is independently selected from any one of H, C1-C50 linear or branched alkyl groups (specifically, methyl, t-butyl and hexyl), C1-C50 alkoxy groups (specifically, methoxy, t-butoxy and hexyloxy), C6-C50 aralkyl groups (specifically, t-butylphenyl and trimethylphenyl), and C1-C50 heteroalkyl groups (specifically, trimethylsilyl and triisopropylsilylethynyl);
R 1 -R 4 each independently selected from any one of H, C1 to C50 linear or branched alkyl groups (specifically, methyl, t-butyl and hexyl), C1 to C50 alkoxy groups (specifically, methoxy, t-butoxy and hexyloxy), C6 to C50 aralkyl groups (specifically, t-butylphenyl and trimethylphenyl), and C1 to C50 heteroalkyl groups (specifically, trimethylsilyl and triisopropylsilylethynyl).
The seven-membered ring-containing conjugated compound represented by the above formula I based on the quinoid structure is prepared according to the reaction scheme shown in FIG. 1 by a method comprising the steps of:
1) under the protection of inert gas, under the existence of a catalyst and a ligand, carrying out Suzuki coupling reaction on halogenated polycyclic aromatic hydrocarbon shown in a formula 2, boric acid of aromatic hydrocarbon shown in a formula 3 and alkali in an organic solvent to obtain an aromatic hydrocarbon substituted phenyl diketone compound shown in a formula 4;
in the formula 2, X can be a halogen atom, and can be selected from any one of fluorine, chlorine, bromine and iodine;
in the formula 3, Ar represents a polycyclic aromatic hydrocarbon structure containing at least one aromatic ring independently selected from any one of an aryl group, a heteroaryl group, a substituent-containing aryl group and a substituent-containing heteroaryl group, and the bonding mode of the inside of the group is selected from at least one of a single bond, a double bond, a triple bond and fusion;
the substituent in the aryl group containing the substituent and the heteroaryl group containing the substituent can be any one of a linear or branched alkyl group of C1-C50, an alkoxy group of C1-C50, an aralkyl group of C6-C50 and a heteroalkyl group of C1-C50;
specifically, the compound represented by the formula 3 may be selected from any one of the following structural formulas 31 to 45:
in the above chemical formulas 31 to 45, R may be any one selected from the group consisting of H, C1 to C50 linear or branched alkyl groups (specifically, methyl, t-butyl and hexyl groups), C1 to C50 alkoxy groups (specifically, methoxy, t-butoxy and hexyloxy groups), C6 to C50 aralkyl groups (specifically, t-butylphenyl and trimethylphenyl groups), and C1 to C50 heteroalkyl groups (specifically, trimethylsilyl and triisopropylsilylethynyl groups);
in the formula 4, Ar is the same as Ar in the formula 3;
the structural formula of the arene-substituted phenyl diketone compound shown in the formula 4 is shown as 46-60:
r in the compounds 46 to 60 is the same as R in the compounds 1 to 15;
2) under the protection of inert gas and in the presence of alkali, conducting an Aldo condensation reaction on an aromatic substituted phenyl diketone compound shown as a formula 4 and p-toluenesulfonic acid monohydrate in an organic solvent to obtain a polycyclic aromatic hydrocarbon compound BDH containing a seven-membered ring shown as a formula 5;
in the formula 5, Ar is the same as Ar in the formula 2;
the compound represented by formula 5 may be selected from any one of the following structural formulae 61 to 75:
r in the above compounds 61 to 75 is the same as R in the above compounds 1 to 15;
3) under the protection of inert gas, carrying out Diels-Alder reaction on the polycyclic aromatic hydrocarbon compound BDH containing the seven-membered ring shown in the formula 5, the polysubstituted halogenated o-xylene shown in the formula 6 and NaI in an organic solvent to obtain the polycyclic aromatic hydrocarbon compound BHH containing the seven-membered ring shown in the formula 7;
in the formula 6, X may be a halogen atom, specifically, may be any one selected from fluorine, chlorine, bromine, and iodine;
R 1 -R 4 each of which isIndependently selected from any one of H, C1-C50 linear or branched alkyl (specifically, methyl, tert-butyl and hexyl), C1-C50 alkoxy (specifically, methoxy, tert-butoxy and hexyloxy), C6-C50 aralkyl (specifically, tert-butylphenyl and trimethylphenyl) and C1-C50 heteroalkyl (specifically, trimethylsilyl and triisopropylsilylethynyl);
in the formula 7, Ar is the same as Ar in the formula 2; r 1 -R 4 In the same formula 6R 1 -R 4 ；
The compound represented by formula 7 may be selected from any one of the following structural formulas 76 to 90,
r in the compounds 76 to 90 is the same as R in the compounds 1 to 15;
4) carrying out nucleophilic addition reaction on the polycyclic aromatic hydrocarbon compound BHH containing the seven-membered ring shown in the formula 7, a Grignard reagent or a butyl lithium reagent in an organic solvent under the protection of inert gas to obtain a substituted polycyclic aromatic hydrocarbon compound BHH-OH shown in a formula 8;
in the formula 8, Ar is the same as Ar, R in the formula 3 1 -R 4 In the same formula 6R 1 -R 4 (ii) a R on the seven-membered ring is any one of linear or branched alkyl groups (specifically, methyl, tert-butyl and hexyl) selected from H, C1-C50, alkoxy groups (specifically, methoxy, tert-butoxy and hexyloxy) of C1-C50, aralkyl groups (specifically, tert-butylphenyl and trimethylphenyl) of C6-C50 and heteroalkyl groups (specifically, trimethylsilyl and triisopropylsilylethynyl) of C1-C50, specifically, triisopropylsilylethynyl;
5) under the protection of inert gas, the substituted polycyclic aromatic hydrocarbon compound BHH-OH shown in the formula 8 and stannous chloride dihydrate are subjected to reduction reaction in an organic solvent to obtain the polycyclic aromatic hydrocarbon compound BHHQ containing the heptatomic ring based on the quinoid structure shown in the formula I.
In step 1) of the above method, the inert gas may be specifically nitrogen;
the catalyst consists of a palladium catalyst and a ligand,
wherein the palladium catalyst is at least one selected from palladium tetrakistriphenylphosphine, palladium chloride, palladium acetate, 1, 4-bis (diphenylphosphinobutane) palladium dichloride, bis (di-tert-butylphenyl) palladium, bis (dibenzylideneacetone) palladium and bis (triphenylphosphine) palladium dichloride, and specifically can be palladium acetate;
the ligand is selected from at least one of 1,2,3,4, 5-pentaphenyl-1 '- (di-tert-butylphosphine) ferrocene, 2-2' -bipyridyl, 2-tert-butylphosphine-10 phenylindole, N-phenyl-2- (di-tert-butylphosphine) pyrrole, triphenylphosphine, 3,4,7, 8-tetramethyl-1, 10-phenanthroline, (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl, (2-disubstituted phosphino-phenyl) -1-alkyl-indolylphosphine and 2- (di-tert-butylphosphine) -1-phenylpyrrole, and specifically can be 2-tert-butylphosphine-10 phenylindole;
the alkali can be at least one selected from sodium acetate, potassium acetate, cesium acetate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, potassium fluoride, sodium carbonate, cesium carbonate and cesium fluoride, and specifically can be potassium fluoride;
the molar ratio of the halogenated polycyclic aromatic hydrocarbon shown in the formula 2, the borate of the aromatic hydrocarbon shown in the formula 3, the alkali, the palladium catalyst and the ligand can be 1: 1-5: 5-10: 0.1-0.2: 0.1-2.0, specifically 1:2.8:6.0:0.15: 0.3;
the reaction temperature of the Suzuki coupling reaction can be 30-100 ℃, specifically 40 ℃, and the reaction time can be 12-72 hours, specifically 72 hours;
the organic solvent can be at least one selected from o-dichlorobenzene, o-xylene, chlorobenzene, tetrahydrofuran, toluene, cyclohexane and 1, 4-dioxane;
the method also comprises the following operations after the Suzuki coupling reaction is completed: adding silica gel powder into a system subjected to Suzuki coupling reaction, rotating a solvent by using a rotary evaporator, and separating and purifying the solid by using a column chromatography method to obtain the aromatic substituted phenyl diketone compound shown in the formula 4.
In step 2) of the above method, the inert gas may be specifically nitrogen;
the alkali can be at least one selected from sodium hydroxide, potassium acetate, cesium acetate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, potassium fluoride, sodium carbonate, cesium carbonate, and cesium fluoride, and specifically can be sodium hydroxide;
the aromatic hydrocarbon-substituted phenyl dione compound represented by formula 4, the base, and the p-toluenesulfonic acid monohydrate may have a molar ratio of 1: 0.1-5: 0.1-2.0, specifically 1:0.4: 0.2;
the reaction temperature of the Aldo condensation reaction can be 30-100 ℃, specifically 80 ℃, and the reaction time can be 3-12 hours, specifically 6 hours;
the organic solvent can be at least one selected from o-dichlorobenzene, o-xylene, chlorobenzene, tetrahydrofuran, toluene, cyclohexane and 1, 4-dioxane;
the method also comprises the following operations after the Aldo condensation reaction: and filtering the system after the Aldo condensation reaction, and washing the solid for multiple times by using solvents such as methanol, water, acetone and the like to obtain the polycyclic aromatic hydrocarbon compound BDH containing the seven-membered ring shown in the formula 5.
In step 3), the inert gas may be nitrogen;
the mol ratio of the polycyclic aromatic hydrocarbon compound BDH containing seven-membered rings shown in the formula 5 to the polysubstituted halogenated o-xylene shown in the formula 6 to the NaI can be 1: 1-20: 5-20, specifically 1:6: 13;
the reaction temperature of the Diels-Alder reaction can be 100-200 ℃, specifically 160 ℃, and the reaction time can be 12-100 h, specifically 72 h;
the organic solvent can be at least one selected from o-dichlorobenzene, o-xylene, chlorobenzene, tetrahydrofuran, toluene, cyclohexane and 1, 4-dioxane;
the Diels-Alder reaction also comprises the following operations: and adding sodium bisulfite aqueous solution and DCM into the system after the Diels-Alder reaction for extraction, collecting an organic phase, concentrating, filtering, and washing the obtained solid for multiple times by using solvents such as methanol, water, acetone and the like to obtain the polycyclic aromatic hydrocarbon compound BHH containing the seven-membered ring shown in the formula 7.
In the step 4), the inert gas may be nitrogen;
the Grignard reagent or the butyl lithium reagent refers to a Grignard reagent of polycyclic aromatic hydrocarbon or a butyl lithium reagent of aliphatic alkane, the polycyclic aromatic hydrocarbon compound at least contains one aromatic ring, the aromatic ring is independently selected from any one of aryl, heteroaryl, aryl containing substituent and heteroaryl containing substituent, and the bonding mode of the inner part of the group is selected from at least one of single bond, double bond, triple bond and fusion;
the substituent in the aryl group containing the substituent and the heteroaryl group containing the substituent can be any one of a linear or branched alkyl group of C1-C50, an alkoxy group of C1-C50, an aralkyl group of C6-C50 and a heteroalkyl group of C1-C50;
the molar ratio of the polycyclic aromatic hydrocarbon compound BHH containing the seven-membered ring shown in the formula 7 to the Grignard reagent or the butyl lithium reagent can be 1: 3-12, specifically 1: 6;
the reaction temperature of the nucleophilic addition reaction can be 0-50 ℃, specifically 25 ℃, and the reaction time can be 1-100 hours, specifically 3 hours;
the nucleophilic addition reaction also comprises the following operations: and (3) concentrating the system after the nucleophilic addition reaction, adding an ammonium chloride aqueous solution and dichloromethane for extraction, collecting an organic phase for concentration, and separating by column chromatography to obtain the substituted polycyclic aromatic hydrocarbon compound BHH-OH shown in the formula 8.
In step 5), the inert gas may be nitrogen;
the molar ratio of the substituted polycyclic aromatic hydrocarbon compound BHH-OH shown in the formula 8 to the stannous chloride dihydrate can be 1: 1-10, specifically 1: 4;
the reaction temperature of the reduction reaction can be 0-50 ℃, specifically 25 ℃, and the reaction time can be 1-100 hours, specifically 1-50 hours, 1-25 hours, 1-10 hours or 3 hours;
the organic solvent can be at least one selected from o-dichlorobenzene, o-xylene, chlorobenzene, tetrahydrofuran, toluene, cyclohexane and 1, 4-dioxane;
the method also comprises the following operations after the reduction reaction: and adding water and dichloromethane into the system after the reduction reaction for extraction, collecting an organic phase, concentrating, and separating by column chromatography to obtain the polycyclic aromatic hydrocarbon compound BHHQ containing the seven-membered ring based on the quinoid structure shown in the formula I.
The polycyclic aromatic hydrocarbon compound BDH containing seven-membered rings shown in the formula 5, the polycyclic aromatic hydrocarbon compound BHH containing seven-membered rings shown in the formula 7, the substituted polycyclic aromatic hydrocarbon compound BHH-OH shown in the formula 8 and the polycyclic aromatic hydrocarbon compound BHHQ containing seven-membered rings based on the quinoid structure shown in the formula I, which are prepared by the method, belong to the protection scope of the invention.
The invention also provides application of the polycyclic aromatic hydrocarbon compound BHHQ based on the quinoid structure and containing seven-membered rings in preparation of a field effect device as a p-type semiconductor material.
In the above application, the field effect device includes a field effect transistor; the field effect transistor exhibits p-type transmission properties.
The invention further provides a preparation method of the field effect device, which comprises the following steps: spin-coating a seven-membered ring-containing polycyclic aromatic hydrocarbon compound BHHQ based on a quinoid structure shown in the formula I on a modified sheet to form a film, and preparing the field effect device;
the invention has the following advantages:
the invention designs and synthesizes the polycyclic aromatic hydrocarbon compound BDH containing seven-membered rings shown in the formula 5, the polycyclic aromatic hydrocarbon compound BHH containing seven-membered rings shown in the formula 7, the substituted polycyclic aromatic hydrocarbon compound BHH-OH shown in the formula 8 and the polycyclic aromatic hydrocarbon compound BHHQ containing seven-membered rings based on a quinoid structure shown in the formula I. The synthesized compound has novel structure and simple and easily obtained reaction raw materials. The synthesis of the novel conjugated compound containing the seven-membered ring based on the quinoid structure is successfully realized through five steps of Suzuki coupling reaction, condensation reaction, Diels-Alder reaction, nucleophilic addition reaction and reduction reaction. The reaction yield related to synthesis is high and the operation is simple. The novel conjugated compound containing seven-membered rings based on the quinoid structure is novel in structure, good in stability and good in solubility in common organic solvents. The novel conjugated compound containing seven-membered rings based on the quinoid structure, which is shown in the formula I, has good carrier transmission performance and solubility, is beneficial to preparation of devices, and a field effect transistor prepared by using the novel conjugated compound can show good p-type transmission performance. The novel conjugated compound containing seven-membered rings based on the quinoid structure, disclosed by the invention, has certain solution fluorescence emission and has potential application in fluorescence imaging and detection.
The invention designs and synthesizes a novel conjugated molecular material containing seven-membered rings based on the quinoid structure, and characterizes the properties of absorption, emission, response and the like, and also tests the performance of an organic field effect transistor to show p-type transmission performance.
Drawings
FIG. 1 is a reaction scheme for preparing a seven-membered ring-containing polycyclic aromatic hydrocarbon compound based on a quinoid structure according to the present invention.
FIG. 2 is a reaction equation for preparing a seven-membered ring-containing polycyclic aromatic hydrocarbon compound BHHQ-TIPS based on a quinoid structure shown in formula I from 3-formylthiophene-2-boronic acid in the present invention.
FIG. 3 is a UV-VISIBLE absorption spectrum of the compound BHHQ-TIPS prepared in example 1 in a methylene chloride solution.
FIG. 4 is a cyclic voltammogram of the compound BHHQ-TIPS prepared in example 1.
FIG. 5 is an output curve of BHHQ-TIPS, a compound prepared in example 1.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The invention provides a seven-membered ring conjugated compound based on a quinoid structure, which has a structural formula shown as a formula I:
in the formula I, Ar refers to a polycyclic aromatic hydrocarbon structure, the polycyclic aromatic hydrocarbon structure at least contains one aromatic ring, the aromatic ring is independently selected from any one of aryl, heteroaryl, aryl containing substituent groups and heteroaryl containing substituent groups, and the bonding mode in the group is selected from at least one of single bond, double bond, triple bond and fusion;
the substituent in the aryl group containing the substituent and the heteroaryl group containing the substituent can be any one of a linear or branched alkyl group of C1-C50, an alkoxy group of C1-C50, an aralkyl group of C6-C50 and a heteroalkyl group of C1-C50;
specifically, Ar may be any one of the following 1 to 15:
in the structural formulas 1-15, R can be any one of linear chain or branched chain alkyl of H, C1-C50, alkoxy of C1-C50, aralkyl of C6-C50 and heteroalkyl of C1-C50;
R 1 -R 4 each independently selected from any one of H, C1-C50 straight chain or branched chain alkyl, C1-C50 alkoxy, C6-C50 aralkyl and C1-C50 heteroalkyl;
r on the seven-membered ring in the formula I is any one of linear chain or branched chain alkyl selected from H, C1-C50, alkoxy selected from C1-C50, aralkyl selected from C6-C50 and heteroalkyl selected from C1-C50, and specifically is triisopropylsilylethynyl.
The invention also provides application of the polycyclic aromatic hydrocarbon compound BHHQ containing seven-membered rings based on the quinoid structure shown in the formula I in preparation of a field effect device as a p-type semiconductor material.
In the above application, the field effect device includes a field effect transistor; the field effect transistor exhibits p-type transmission properties.
The invention designs and synthesizes a novel conjugated molecular material containing seven-membered rings based on the quinoid structure, and characterizes the properties of absorption, emission, response and the like, and also tests the performance of an organic field effect transistor to show p-type transmission performance.
Example 1, synthesis of compound 19(BHHQ-TIPS) described by formula I:
the chemical reaction flow chart is shown in fig. 2, and the specific reaction step conditions are as follows:
to a 250ml two-necked flask with a stirrer and a reflux condenser were added compound 34(3.00g,9.15mmol,1.0eq.), KF (5.16g,54.9mmol,6.0eq.), palladium acetate (0.31g,1.37mmol,0.15eq.), 2-tert-butylphosphine-10 phenylindole (0.93g,2.75mmol,0.3eq.) and the air in the system was replaced with nitrogen by the schlenk technique. Then 3-formylthiopheneboronic acid (4.00g,25.6mmol,2.8eq.) dissolved in 60ml of tetrahydrofuran was injected into the system. The system was placed in an oil bath, heated to 40 ℃ and reacted under reflux for 3 days. The reaction was stopped after the completion of the reaction of the starting materials as monitored by TLC. After it had cooled to room temperature, the system was spin dried. Separating by column chromatography, gradient eluting until the polarity of the eluent is petroleum ether: ethyl acetate ═ 20: 1, 493.34 g of compound was isolated as a yellow solid in 96.0% yield
To a 50ml two-necked flask with a stirrer and a reflux condenser was added compound 49(1.53g,4.0mmol,1.0 eq.). Then, about 15ml of tetrahydrofuran was injected into the system at 30 ℃ until the compound 49 was completely dissolved. After cooling to room temperature, p-toluenesulfonic acid monohydrate (152mg,0.8mmol,0.2eq.) was added to the system, and stirred at room temperature for 10 min. Sodium hydroxide (64mg,1.6mmol,0.4eq.) dissolved in 0.6ml of deionized water and 0.6ml of tetrahydrofuran was added dropwise with a dropper. The system is put in an oil bath, the temperature is raised to 80 ℃, and the reflux reaction is carried out for 6 hours. The reaction was stopped after the completion of the reaction of the starting materials was monitored by TLC. After the mixture is cooled to room temperature, the system is directly filtered, washed by methanol, acetone and water acetone in sequence, and a yellow solid compound 64BDH is obtained quantitatively
Compound 64(346mg,1mmol,1.0eq.) and α, α, α ', α' -tetrabromo-xylene (2.53g,6.0mmol,6.0eq.), NaI (1.94g,13mmol,13.0eq.) were added to a 100ml reaction tube with a stirrer, and the air in the system was replaced with nitrogen gas using the schlenk technique. Then, 30ml of N, N-dimethylacetamide was injected into the system. The system was placed in an oil bath which had been warmed to 160 ℃ and heated to react for 3 days. The reaction was stopped after the completion of the reaction of the starting materials as monitored by TLC. After it was cooled to room temperature, NaHSO was added 3 Until no more precipitate is precipitated. An appropriate amount of dichloromethane was added for extraction, and the organic phase (lower layer, brown) was collected and washed three times with water. The organic phase was concentrated using a rotary evaporator, filtered, and the solid was washed with methanol, acetone, water, and acetone in this order to give 79BHH 397mg as a yellow solid with a yield of 72.7%.
The atmosphere in a 100ml two-necked flask with a stirrer was replaced with nitrogen using the schleck technique, and triisopropylsilylacetylene (0.59ml,2.64mmol,7.2eq.) and 45ml of freshly distilled tetrahydrofuran were injected using a syringe. The system was placed in an ice-water bath, n-butyllithium (1.37ml,2.20mmol,6.0eq.) was added dropwise, then the ice-water bath was removed and allowed to slowly return to room temperature, after stirring at room temperature for 1h, compound 79(200mg,0.37mmol,1.0eq.) was added under a nitrogen atmosphere and stirred at room temperature for 3 h. The reaction was stopped after the completion of the reaction of the starting materials as monitored by TLC. The system was concentrated using a rotary evaporator and then NH was added 4 Aqueous Cl and dichloromethane. The combined organic phases were collected and dried over anhydrous sodium sulfate, filtered and spin-dried. Separating the system by column chromatography, and carrying out gradient leaching until the polarity of the leaching agent is increased to the polarity of petroleum ether: 1-dichloromethane: 1, a yellow solid was isolated and washed with petroleum ether and methanol to give 121mg of a white solid. To a 25ml two-necked flask with a stirrer were added the product of the previous step (15mg,0.02mmol,1.0eq.) and SnCl 2 .H 2 O (15mg,0.06mmol,4.0 eq.). The air in the system was replaced with nitrogen by using the Schlenk technique, and 10ml of toluene was injected into the system. The system was left to stir for 3 hours in the dark at room temperature. Gradual purple color change of the solution was observed and the reaction of the starting material was monitored by TLC to be completeAfter completion, the reaction was stopped. 60ml of water is added into the system for dilution, then a proper amount of dichloromethane is added for extraction, an organic phase is collected, dried by anhydrous sodium sulfate, filtered and concentrated. The system is charged with neutral Al 2 O 3 Separating the chromatographic column, and performing gradient elution until the polarity of the eluent is petroleum ether: dichloromethane ═ 4: 1, 14mg of compound 19(BHHQ-TIPS) was isolated as a purple solid, and the yield in the two steps was 35%.
The structure validation data is as follows:
1 H NMR(400MHz,CDCl 3 )：δppm＝8.76(s,2H),8.15(s,2H),8.00(s,2H),7.78(d,J＝10.8,2H),7.72(d,J＝9.2,2H),7.47-7.37(m,8H),1.21(s,42H)；
13 C NMR(175MHz,CD 2 Cl 2 ):δppm＝142.8,140.8,138.2,134.9,132.9,132.5,132.5,131.9,131.5,131.0,130.0,128.1,127.8,127.4,127.2,126.6,126.1,121.7,108.4,104.3,18.7,11.6；
HRMS (MALDI-TOF): calculated value is C 58 H 60 S 2 Si 2 (M + ) 876.3669; mass spectral peak positions: 876.3669.
as can be seen from the above, the product had a correct structure and was Compound 19(BHHQ-TIPS) represented by formula I.
Example 2 uv-vis absorption spectrum of compound BHHQ-TIPS in solution:
the compound BHHQ-TIPS prepared in example 1 of the present invention was dissolved in a methylene chloride solvent (concentration: 10) - 5 mol/L), and the absorption spectrum of BHHQ-TIPS in the solution is shown in FIG. 3. From fig. 3, it can be seen that: the compound BHHQ-TIPS has two absorption peaks respectively distributed in the interval of 250-360nm and 410-640 nm. The maximum absorption wavelength of the compound BHHQ-TIPS is about 556 nm.
Example 3 measurement of electrochemical properties and front-line orbital levels (LUMO and HOMO) of compounds using electrochemical cyclic voltammetry:
the electrochemical characteristics of the compound BHHQ-TIPS in the embodiment 1 of the invention were tested by using an electrochemical workstation, using ferrocene as a standard, tetrabutylammonium hexafluorophosphate as an electrolyte, and tetrabutylhexakis as an electrolyteAmmonium fluorophosphate in dichloromethane (0.1M concentration). The test is carried out by adopting a standard three-electrode system, a glassy carbon electrode is taken as a working electrode, a platinum wire is taken as a counter electrode, and Ag/Ag + As a reference electrode. The cyclic voltammogram is shown in FIG. 4, and it can be seen from FIG. 4 that: the compound BHHQ-TIPS has two reversible reduction peaks, and the initial reduction peak potentials are about 1.04eV and-1.18 eV respectively. The compound BHHQ-TIPS has two strong oxidation peaks, the initial oxidation peak potentials are respectively 0.74eV and 1.04eV, and a weak oxidation peak is arranged around 1.58 eV. The LUMO level was calculated to be-3.57 eV, and the HOMO level was calculated to be-5.12 eV.
Example 4 field effect device of the prepared compound:
field effect transistor devices containing gold-electrode bottom-gate-bottom-contacts (BGBC) were modified with Octadecyltrichlorosilane (OTs) monolayers. Then, BHHQ-TIPS (5mg) obtained in inventive example 1 was dissolved in 0.5mL of chloroform, and the resulting solution was spin-coated on the above-modified sheet to form a film (liquid drop volume: 200. mu.L, rotation speed 3000 rpm, time: 1 minute). Preparing a field effect device, and respectively testing the field effect properties of the field effect device under the air and nitrogen atmosphere; the corresponding output curve is shown in fig. 5. The compounds exhibit p-type field effect modulating properties.
Claims (10)
1. A seven-membered ring-containing conjugated compound based on a quinoid structure has a structural formula shown as formula I:
in the formula I, Ar refers to a polycyclic aromatic hydrocarbon structure, the polycyclic aromatic hydrocarbon structure at least contains one aromatic ring, the aromatic ring is independently selected from any one of aryl, heteroaryl, aryl containing substituent groups and heteroaryl containing substituent groups, and the bonding mode in the group is selected from at least one of single bond, double bond, triple bond and fusion;
the substituent in the aryl containing the substituent and the heteroaryl containing the substituent is any one of a linear or branched alkyl group of C1-C50, an alkoxy group of C1-C50, an aralkyl group of C6-C50 and a heteroalkyl group of C1-C50;
R 1 -R 4 each independently selected from any one of H, C1-C50 straight chain or branched chain alkyl, C1-C50 alkoxy, C6-C50 aralkyl and C1-C50 heteroalkyl;
r on the seven-membered ring in the formula I is any one selected from H, C1-C50 straight chain or branched chain alkyl, C1-C50 alkoxy, C6-C50 aralkyl and C1-C50 heteroalkyl.
2. The compound of claim 1, wherein: in formula I, Ar is any one of the following 1-15:
r in the structural formulas 1 to 15 respectively and independently represents any one of linear chain or branched chain alkyl of H, C1-C50, alkoxy of C1-C50, aralkyl of C6-C50 and heteroalkyl of C1-C50.
3. A process for preparing a compound according to claim 1 or 2, comprising the steps of:
1) under the protection of inert gas, under the existence of a catalyst and a ligand, carrying out Suzuki coupling reaction on halogenated polycyclic aromatic hydrocarbon shown in a formula 2, boric acid of aromatic hydrocarbon shown in a formula 3 and alkali in an organic solvent to obtain an aromatic hydrocarbon substituted phenyl diketone compound shown in a formula 4;
in the formula 2, X is a halogen atom, and can be selected from any one of fluorine, chlorine, bromine and iodine;
in the formula 3, Ar is the same as Ar in the formula I in the claim 1;
in the formula 4, Ar is the same as Ar in the formula I in the claim 1;
2) under the protection of inert gas and in the presence of alkali, conducting an Aldo condensation reaction on an aromatic substituted phenyl diketone compound shown as a formula 4 and p-toluenesulfonic acid monohydrate in an organic solvent to obtain a polycyclic aromatic hydrocarbon compound BDH containing a seven-membered ring shown as a formula 5;
in the formula 5, Ar is the same as Ar in the formula I in the claim 1;
3) under the protection of inert gas, carrying out Diels-Alder reaction on a polycyclic aromatic hydrocarbon compound BDH containing a seven-membered ring shown in a formula 5, polysubstituted halogenated o-xylene shown in a formula 6 and NaI in an organic solvent to obtain a polycyclic aromatic hydrocarbon compound BHH containing a seven-membered ring shown in a formula 7;
in the formula 6, X is a halogen atom, and can be selected from any one of fluorine, chlorine, bromine and iodine;
R 1 -R 4 each independently selected from any one of H, C1-C50 straight chain or branched chain alkyl, C1-C50 alkoxy, C6-C50 aralkyl and C1-C50 heteroalkyl;
in the formula 7, Ar is the same as Ar in the formula I in the claim 1; r 1 -R 4 In the same formula 5R 1 -R 4 ；
4) Carrying out nucleophilic addition reaction on the polycyclic aromatic hydrocarbon compound BHH containing the seven-membered ring shown in the formula 7, a Grignard reagent or a butyl lithium reagent in an organic solvent under the protection of inert gas to obtain a substituted polycyclic aromatic hydrocarbon compound BHH-OH shown in a formula 8;
in the formula 8, Ar is the same as Ar, R in the formula 3 1 -R 4 In the same formula 6R 1 -R 4 (ii) a R on the seven-membered ring is a straight chain selected from H, C1-C50Or any one of branched alkyl, alkoxy of C1-C50, aralkyl of C6-C50 and heteroalkyl of C1-C50;
5) under the protection of inert gas, the substituted polycyclic aromatic hydrocarbon compound BHH-OH shown in the formula 8 and stannous chloride dihydrate are subjected to reduction reaction in an organic solvent to obtain the polycyclic aromatic hydrocarbon compound BHHQ containing the seven-membered ring based on the quinoid structure shown in the formula I in claim 1.
4. A polycyclic aromatic hydrocarbon compound having a seven-membered ring represented by formula 5 in claim 3.
5. A polycyclic aromatic hydrocarbon compound having a seven-membered ring represented by formula 7 in claim 3.
6. A substituted polycyclic aromatic hydrocarbon compound represented by the formula 8 in claim 3.
7. Use of a polycyclic aromatic hydrocarbon compound containing a seven-membered ring based on a quinoid structure shown in formula I in claim 1 as a p-type semiconductor material in the preparation of a field effect device.
8. Use according to claim 7, characterized in that: in the application, the field effect device comprises a field effect transistor, and the field effect transistor shows p-type transmission performance.
9. A field effect device using a polycyclic aromatic hydrocarbon compound containing a seven-membered ring based on a quinoid structure shown in formula I in claim 1 as a p-type semiconductor material.
10. A method of making a field effect device as claimed in claim 9, comprising the steps of: and (2) spin-coating a seven-membered ring-containing polycyclic aromatic hydrocarbon compound based on a quinoid structure shown in formula I in the formula 1 on the modified sheet to form a film, so as to prepare the field effect device.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007223904A (en) * | 2005-02-15 | 2007-09-06 | Tosoh Corp | pi-CONJUGATED COMPOUND HAVING CARDO STRUCTURE, PROCESS FOR PREPARING THE SAME AND USE THEREOF |
| US20140011973A1 (en) * | 2012-07-05 | 2014-01-09 | Boe Technology Group Co., Ltd. | Compound with branching alkyl chains, method for preparing the same, and use thereof in photoelectric device |
| CN106046328A (en) * | 2016-01-26 | 2016-10-26 | 中国科学院化学研究所 | Silane-substituted two-dimensional conjugated polymer and preparation method thereof, and application of silane-substituted two-dimensional conjugated polymer to photovoltaic device |
| CN109438496A (en) * | 2018-11-19 | 2019-03-08 | 哈尔滨工业大学 | A kind of pi-conjugated compound, preparation method and its application based on bithiophene |
| CN109748925A (en) * | 2017-11-03 | 2019-05-14 | 中国科学院化学研究所 | The aromatic condensed ring structure unit and its synthetic method and application that a kind of alkoxy replaces |
| CN111187399A (en) * | 2020-02-26 | 2020-05-22 | 中国科学院化学研究所 | Near-infrared light-controlled bistable field effect transistor polymer and preparation method and application thereof |
-
2021
- 2021-03-29 CN CN202110333429.2A patent/CN115124561A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007223904A (en) * | 2005-02-15 | 2007-09-06 | Tosoh Corp | pi-CONJUGATED COMPOUND HAVING CARDO STRUCTURE, PROCESS FOR PREPARING THE SAME AND USE THEREOF |
| US20140011973A1 (en) * | 2012-07-05 | 2014-01-09 | Boe Technology Group Co., Ltd. | Compound with branching alkyl chains, method for preparing the same, and use thereof in photoelectric device |
| CN106046328A (en) * | 2016-01-26 | 2016-10-26 | 中国科学院化学研究所 | Silane-substituted two-dimensional conjugated polymer and preparation method thereof, and application of silane-substituted two-dimensional conjugated polymer to photovoltaic device |
| CN109748925A (en) * | 2017-11-03 | 2019-05-14 | 中国科学院化学研究所 | The aromatic condensed ring structure unit and its synthetic method and application that a kind of alkoxy replaces |
| CN109438496A (en) * | 2018-11-19 | 2019-03-08 | 哈尔滨工业大学 | A kind of pi-conjugated compound, preparation method and its application based on bithiophene |
| CN111187399A (en) * | 2020-02-26 | 2020-05-22 | 中国科学院化学研究所 | Near-infrared light-controlled bistable field effect transistor polymer and preparation method and application thereof |
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