CN109438496B - 一种基于并噻吩的π共轭化合物、其制备方法及其应用 - Google Patents
一种基于并噻吩的π共轭化合物、其制备方法及其应用 Download PDFInfo
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- CN109438496B CN109438496B CN201811377721.9A CN201811377721A CN109438496B CN 109438496 B CN109438496 B CN 109438496B CN 201811377721 A CN201811377721 A CN 201811377721A CN 109438496 B CN109438496 B CN 109438496B
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- bithiophene
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 56
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000000203 mixture Substances 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-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
- 238000009826 distribution Methods 0.000 claims description 4
- 230000026030 halogenation Effects 0.000 claims description 4
- 238000005658 halogenation reaction Methods 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 12
- 230000005540 biological transmission Effects 0.000 abstract description 9
- 125000006615 aromatic heterocyclic group Chemical group 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 52
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 42
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 34
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 23
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 14
- 239000012074 organic phase Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 12
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000012044 organic layer Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 238000010898 silica gel chromatography Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000010791 quenching Methods 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000005669 field effect Effects 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[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.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 4
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- -1 na (Na)2CO3 Chemical compound 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 4
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 229940126543 compound 14 Drugs 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 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 3
- 238000005406 washing Methods 0.000 description 3
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- WDYVUKGVKRZQNM-UHFFFAOYSA-N 6-phosphonohexylphosphonic acid Chemical compound OP(O)(=O)CCCCCCP(O)(O)=O WDYVUKGVKRZQNM-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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- 125000004429 atom Chemical group 0.000 description 2
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- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- KQIADDMXRMTWHZ-UHFFFAOYSA-N chloro-tri(propan-2-yl)silane Chemical compound CC(C)[Si](Cl)(C(C)C)C(C)C KQIADDMXRMTWHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
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- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 239000000411 inducer Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- 239000012265 solid product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DZEFNRWGWQDGTR-UHFFFAOYSA-N tetradec-1-yne Chemical compound CCCCCCCCCCCCC#C DZEFNRWGWQDGTR-UHFFFAOYSA-N 0.000 description 2
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- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 1
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- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
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- C07F7/02—Silicon compounds
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- 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
- C07F7/0816—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 said ring comprising Si as a ring atom
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- C07F7/02—Silicon compounds
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- C07F7/0803—Compounds with Si-C or Si-Si linkages
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Abstract
Description
技术领域
本发明属于有机半导体材料与半导体光电器件领域,涉及一种π-共轭化合物、其制备方法及其应用,具体涉及一种基于并噻吩的π共轭化合物、其制备方法及其应用。
背景技术
有机半导体材料广泛用于有机场效应晶体管(OFETs),有机发光二极管(OLEDs)和有机太阳能电池(OSCs)。其中,多环芳烃中的共轭直链分子因其具有巨大的π电子共轭体系、良好的平面性,使这些材料具有优良的载流子迁移率和消光系数,是有机半导体材料中不可或缺的材料,也具有整体线性形状的噻吩稠环分子是最有希望的有机半导体材料候选物之一。在固态状态下,噻吩稠环分子倾向于形成合适的固态结构,这适合于有机半导体器件中的有效电荷传输。此外,硫原子的掺入被认为通过相邻部分之间的S-S和S-π相互作用产生了有利的轨道重叠。噻吩中S原子的密集度较高且具有较高的极化度,分子间容易形成多重S-S、S-C相互作用,并且能够增加有效的分子轨道重叠,有利于载流子的传输。虽然已经确定引入噻吩结构的稠环直链分子具有良好的光电性能,但目前所报道的已合成长链分子结构并不多,且存在研究进展缓慢、合成方法复杂、产率低、性能差等问题。
发明内容
为了克服上述问题,通过设计分子结构、引入或调整相关官能团来控制其半导体性质,本发明提供了一种基于并噻吩的π共轭化合物,该化合物作为半导体材料具有良好的溶解性能和优异的电荷传输性能。
具体技术方案如下:
一种基于并噻吩的π共轭化合物,所述π共轭化合物包括并噻吩并二邻烷基苯形成的长链共轭单元,所述长链共轭单元为至少11个芳香环或芳香杂环或芳香稠环单元以π-共轭相连的方式串联形成的共轭单元:
所述π共轭化合物具有下式(I)所示的分子结构:
其中,R1、R2为含碳原子数为3-12的直链或支链的烷基,R1与R2的含碳原子数相同或不同;
Y为氢原子、溴原子、氰基、三甲基硅烷基或三异丙基硅烷基;
X为含烷基支链的硅原子、硫原子、氮原子、硼原子或酮羰基、丙二氰基团、苯环,其与碳碳双键相连形成五元芳香杂环或多元芳香稠环结构。
上述并噻吩的π共轭化合物具有一维线性结构,长链共轭单元为至少11个芳香环或芳香杂环或芳香稠环单元以π-共轭相连的方式串联形成的共轭单元,扩展共轭面积。
更进一步地,所述π共轭化合物具有下式(II)所示的分子结构:
其中,R1、R2为含碳原子数为3-12的直链或支链的烷基,R1与R2的含碳原子数相同或不同;
Y为氢原子、溴原子、氰基、三甲基硅烷基或三异丙基硅烷基;
X为Si原子、—C=C—,其与碳碳双键相连形成双五元芳香杂环或多元芳香稠环结构。
上述并噻吩的π共轭化合物在增加共轭面积的基础上,分子还具有空间非平面性结构,为该化合物提供了多一个维度的电荷传输通道,从而更有利于电荷在体相内的传输。
更进一步的,所述R1、R2为相同碳原子数的直链烷基。最优选的,所述R1、R2为十二烷基。
更进一步的,所述Y为三甲基硅烷基。
本发明所设计的π共轭化合物的分子结构是单一确定的,因而具有单一分子量分布特性。与分子量分布较宽的高分子有机共轭聚合物相比具有结构明确、材料易于纯化、以及更加良好的可重复性能等优势。
本发明还提供了一种组合物,该组合物中包括上述π-共轭化合物。
本发明的另一目的还在于提供一种制备所述π共轭化合物的方法,该方法包括以下关键步骤:
S1:以噻吩并[3,2-b]噻吩和双烷基双硼酸酯为原料通过卤代、偶联反应合成中间体,中间体结构如下式(III):
其中:
R1、R2为含碳原子数为3-12的直链或支链的烷基,R1与R2的含碳原子数相同或不同;
Y为氢原子、溴原子、氰基、三甲基硅烷基或三异丙基硅烷基;
Z为卤素原子,氯、溴或碘;
S2:上述中间体通过Suzuki偶联反应制备π-共轭化合物。
反应具体步骤如下:
其中,R1、R2为含碳原子数为3-12的直链或支链的烷基,R1与R2的含碳原子数相同或不同;
Y为氢原子、溴原子、氰基、三甲基硅烷基或三异丙基硅烷基;
Z为氯原子、溴原子或碘原子。
S2:以中间体为原料通过Suzuki偶联或取代反应制备π-共轭化合物。通过Suzuki偶联下形成苯环结构;二烷基二卤硅烷、四卤硅烷、硼酸二甲酯、烷基胺等发生取代反应,关环形成杂环结构。
所述方法中采用的偶联反应包括LDA诱导氢迁移偶联反应和钯催化Suzuki偶联反应。
更具体的,利用上述LDA诱导氢迁移偶联反应制备化合物时:
诱导剂为二异丙基氨基锂,溶剂为常规有机溶剂,最好四氢呋喃,所述诱导剂的加入量为原料化合物摩尔量的1.5~4倍;偶联剂为无水氯化铜,所述偶联剂的加入量为原料化合物摩尔量的1.5~4倍;反应温度为-78~25℃,反应时间为24小时。
更具体的,利用上述钯催化Suzuki偶联反应制备化合物时:
在碱性溶剂环境下,在金属催化剂条件下,所述金属催化剂加入量为原料化合物摩尔量的7%~10%;反应温度为80℃~110℃,反应时间为12~36小时。
所述的金属催化剂指的是可溶性的金属钯或镍配合物,优选的催化剂为Pd配合物,包括:Pd(PPh3)4,Pd(OAc)2,Pd(PPh3)2Cl2,Pd2dba3,Pd2dba3·CHCl3,Pd(dppf)Cl2,更优选的催化剂为Pd(PPh3)4,Pd2dba3·CHCl3,Pd(dppf)Cl2。当选用不含配体的Pd催化剂Pd2dba3或Pd2dba3·CHCl3时,催化体系中还需要添加磷配体,以提高反应效率,所述的磷配体包括:PPh3或HP(tBu)3BF4,磷配体与催化剂Pd原子的摩尔比例为2:1。
当选用Suzuki催化缩合制备方法时,反应体系中需要加入无机金属碱溶液。所述的金属碱包括氢氧化物,例如:NaOH,KOH,LiOH,Ba(OH)2,醇盐,例如:NaOEt,KOEt,LiOEt,KOMe,NaOMe,碳酸盐,如:Na2CO3,NaHCO3,K2CO3,KHCO3,磷酸盐,例如:K3PO4,K2HPO4,或者羧酸盐,如:KOAc,NaOAc。上述金属碱通常制备成2M的水溶液,与反应溶剂按一定的体积比例加入到反应体系中,所述的比例为1:2-1:5,优选比例为1:4。
所述溶剂包括烷烃,例如:戊烷、己烷、庚烷、环己烷,芳香溶剂,例如:甲苯、二甲苯,或者醚类溶剂,例如:乙二醇二甲醚、四氢呋喃、1,4-二氧六环,或者极性溶剂,例如:DMF,DMSO。优选的溶剂为四氢呋喃或甲苯。
反应的后处理可采用常规的方式处理,包括:稀释、沉淀、过滤、萃取、淋洗、重结晶、柱层析或/和升华等。一个典型的后处理方案如下:反应结束后,向反应液中加入一定的有机溶剂,萃取分离有机相,用饱和氯化钠溶液水洗有机相三次,合并有机相,用无水硫酸钠干燥有机相,过滤,旋转蒸发除去溶剂,用洗脱剂淋洗硅胶色谱柱分离产物。所述的有机溶剂通常用可溶解本发明化合物的溶剂,例如:氯仿、乙酸乙酯、二氯甲烷、N,N-二甲基甲酰胺、甲苯。所述的洗脱剂为乙酸乙酯与石油醚的混合溶剂,混合比例根据本领域众所周知的方案进行调整。
本发明也提供了按上述合成方法所制备的π-共轭化合物。
本发明还提供了上述π-共轭化合物于制备有机电子器件中的应用。
通过卤代、LDA诱导氢迁移偶联反应和钯催化Suzuki偶联反应能够简易的合成本发明所设计的具有单一分子量分布的含11个芳香环或芳香杂环或芳香稠环单元以π-共轭相连的方式串联形成长链共轭单元的π共轭化合物。该化合物增加了分子的平面性和π-共轭体系电荷密度,对于具有正交结构的,还能够提供了更多维度的电荷传输通道,从而更有利于电荷在体相内的传输。
附图说明
图1化合物6(中间体)的合成;
图2有机薄膜场效应晶体管器件结构。
具体实施方式
下面结合附图和实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
合成所用的玻璃仪器均经过严格清洗干燥。除非特别说明,本发明实施案例中所用的有机溶剂为普通化学纯试剂。噻吩并[3,2-b]噻吩、十四炔、联硼酸频哪醇硼酯、正丁基锂、二异丙基氨基锂、三氟化硼乙醚、三甲基氯硅烷、三异丙基氯硅烷、氯化铜、N,N’-二甲基甲酰胺、四氯化硅、N-溴代丁二酰亚胺,Pd(dppf)Cl2、Pd(PPh3)4、K2CO3、NaHCO3、NH4Cl等原料购自innochem、安耐吉、或国药集团化学试剂有限公司。
实施例1
2,2’-二溴代-联二并噻吩并二烷基苯(化合物6的)合成:
如图1所示,该化合物的合成包括以下步骤:
S1:化合物1的合成
噻吩并[3,2-b]噻吩(5g,35.7mmol),加100mL无水四氢呋喃溶解,氩气保护下冰水浴冷却至0℃,搅拌30分钟,缓慢滴加正丁基锂(35.7mL,2.5M),溶液从浅黄色渐渐变成橙黄、酒红、紫色、黑褐色、棕色最终变为灰粉色,搅拌1小时后,再缓慢滴加三甲基氯化硅(11.57mL,0.11mol),溶液从灰绿色浑浊变为棕色再到墨绿色,冰浴下搅拌10分钟后,移出置于室温继续搅拌4小时,体系由墨绿色逐渐颜色变浅,经过透明黄绿色,最后为透明黄色。用水淬灭后用二氯甲烷萃取混合物,饱和氯化钠水溶液洗三次,用无水硫酸钠干燥有机相,过滤,收集滤液,除去溶剂。用硅胶色谱柱分离纯化混合物,用石油醚淋洗,得到白色固体8.7g,产率85.95%。1H NMR(400MHz,CDCl3),δ:7.35(s,2H),0.37(s,18H)ppm。13C NMRδ:146.73,144.97,125.37ppm。
S2:化合物2的合成
化合物1(1g,35.1mmol)用20mL氯仿溶解,称取NBS(687.9mg,38.6mmol),溶解于9.6mL冰醋酸和12mL氯仿中,将NBS溶液加入常压滴液漏斗中,调整旋塞,以1滴每秒的速度缓慢匀速滴入1的氯仿溶液中。常温搅拌2小时。注意用漏斗滴加时一定要缓慢,否则容易生成双边被溴取代产物。用水淬灭后用二氯甲烷萃取混合物,饱和氯化钠水溶液洗三次,用无水硫酸钠干燥有机相,过滤,收集滤液,除去溶剂。用硅胶色谱柱分离纯化混合物,用石油醚淋洗,得到淡黄色透明油状产物,产率98%。1H NMR(400MHz,CDCl3),δ7.28(s,1H),7.27(s,1H),0.38(s,9H)ppm。
S3:化合物3的合成
化合物2(175mg,0.6mmol)溶于10mL无水四氢呋喃,在氩气氛围下-78℃冷却30分钟,缓慢滴加LDA(0.45mL,0.90mmol),溶液从浅黄色变为金黄色,-78℃保持30分钟,加入CuCl2(121.13mg,0.90mmol)同时鼓氩气,体系变为深棕色,加入完毕后低温反应10min,移至室温搅拌过夜,体系最后为浑浊墨绿色。用水淬灭后用二氯甲烷萃取混合物,饱和氯化钠水溶液洗三次,用无水硫酸钠干燥有机相,过滤,收集滤液,除去溶剂。用硅胶色谱柱分离纯化混合物,用石油醚淋洗,得到黄色固体8.7g,产率51.78%。1H NMR(400MHz,CDCl3),δ7.35(s,2H),0.37(s,18H)ppm。13C NMR(150MHz),δ145.79,145.56,139.92,131.03,125.99,125.11,104.97ppm。MALDI-TOF MS:计算[M]:m/z=577.84,测试[M]:m/z=577.8。
S4:双烷基双硼酸合成
将1-十四炔(1.5mL,6.13mmol)及六甲基磷酰三胺(HMPA)(1.11mL,6.43mmol)溶于干燥的四氢呋喃中,氩气保护,在室温下冷却至-60℃时将n-BuLi(3.81mL,6.128mmol)逐滴加入,在此温度下反应15min,后转移至室温反应30min。紧接着将体系中缓慢加入1-溴十二烷(1.46mL,6.13mmol)并加热到60℃回流2.5小时,恢复室温后用2M HCl溶液淬灭反应。用乙酸乙酯萃取,饱和氯化钠水溶液洗三次,用无水硫酸钠干燥有机相,过滤,收集滤液,除去溶剂。湿法装柱,使用2%三乙胺处理过的硅胶装柱,中和硅胶的酸性,防止酸性的硅胶将产物氧化。用石油醚作为淋洗剂。产物为无色透明半固体半油状物质,产率72%。1H NMR(400MHz,CDCl3),δ7.49(s,1H),3.23(t,4H),0.90(t,6H)。
将联硼酸频那醇酯(2.13g,5.88mmol)、双十二烷基炔烃(2.93g,11.52mmol)及四三苯基磷铂(0.42g,0.34mmol)加入到100mL双口瓶中,抽换氩气三次。加入50mL鼓泡30分钟后的DMF(N,N-二甲基甲酰胺),抽换气,加热12小时后反应结束,用水淬灭后用乙酸乙酯萃取混合物,饱和氯化钠水溶液洗三次,用无水硫酸钠干燥有机相,过滤,收集滤液,除去溶剂。用硅胶色谱柱分离纯化混合物,用石油醚:乙酸乙酯=20:1作为淋洗剂。产物为浅黄色透明半固体半油状物质(yield:85%)。反应完的粗产物在TLC板上254nm及365nm紫外光下均看不到颜色,用碘缸使产物及杂质在TLC板上氧化显色。1H NMR(400MHz,CDCl3),δ7.49(s,1H),3.23(t,4H),0.90(t,6H).
S5:化合物4的合成
将化合物3(100mg,0.17mmol)和合成的双硼酸酯(148.68mg,0.24mmol)加入到100mL双口瓶中抽换气除净其中的氧气,迅速称取Pd(PPh3)4(19.81mg,0.017mmoL),将其在反应体系通氩气的情况下加入,迅速抽换气排尽体系中氧气。将2mol/L K2CO3溶液(0.9mL,1.8mmoL)、10mL四氢呋喃分别氩气鼓泡30分钟后加入反应体系,90℃回流12小时,反应过程中溶液从淡黄色直到反应结束变为澄清棕色。用水淬灭后用二氯甲烷萃取混合物,饱和氯化钠水溶液洗三次,用无水硫酸钠干燥有机相,过滤,收集滤液,除去溶剂。用硅胶色谱柱分离纯化混合物,用石油醚淋洗,得到黄色固体94mg,产率70.5%。1H NMR(400MHz,CDCl3),δ7.48(s,2H),3.23(t,4H),0.91(t,8H),0.44(s,18H)ppm。13C NMR(150MHz),δ144.58,140.40,137.91,135.34,131.63,130.57,126.10ppm。MALDI-TOF MS:计算[M]:m/z=782.39,测试[M]:m/z=782.29。
S6:化合物5的合成
化合物4(100mg,0.13mmol)用5ml氯仿溶解,称取NBS(28.43mg,0.38mmol),溶解于1.6mL冰醋酸和2mL氯仿中,将NBS溶液加入常压滴液漏斗中,调整旋塞,以1滴每秒的速度缓慢匀速滴入化合物4的氯仿溶液中。常温搅拌2小时。注意用漏斗滴加时一定要缓慢,否则容易生成双边被溴取代产物。用水淬灭后用二氯甲烷萃取混合物,饱和氯化钠水溶液洗三次,用无水硫酸钠干燥有机相,过滤,收集滤液,除去溶剂。用硅胶色谱柱分离纯化混合物,用石油醚淋洗,得到淡黄色固体产物,产率90%。1H NMR(400MHz,CDCl3),δ7.47(s,1H),7.3(s,1H),3.20(t,4H),3.09(t,4H),0.92(t,16H),0.45(s,9H)ppm。13C NMR(150MHz),δ144.84,140.22,137.90,134.99,134.75,134.66,133.53,131.93,131.27,130.88,130.62,125.98,122.71,113.92ppm。MALDI-TOF MS:计算[M]:m/z=788.26,测试[M]:m/z=788.3。
S7:化合物6的合成
化合物5(50mg,0.06mmol)溶于5ml无水THF,在氩气氛围下-78℃冷却30分钟,缓慢滴加LDA(0.14mL,0.25mmol),溶液从浅黄色变为亮红色,-78℃保持30分钟,加入CuCl2(37mg,0.25mmol)同时鼓氩气,体系变为葡萄红色,加入完毕后低温反应10分钟,体系转变为棕色,移至室温搅拌过夜,体系最后为浑浊墨绿色。用水淬灭后用二氯甲烷萃取混合物,饱和氯化钠水溶液洗三次,用无水硫酸钠干燥有机相,过滤,收集滤液,除去溶剂。用硅胶色谱柱分离纯化混合物,用石油醚淋洗,得到金黄色油性固体6,产率56%。1H NMR(400MHz,CDCl3),δ7.42(s,1H),3.21(t,4H),3.15(t,4H),0.41(s,9H)ppm。MALDI-TOF MS:计算[M]:m/z=1574.51,测试[M]:m/z=1574.5。
实施例2化合物7合成
在氩气氛下,向6(200mg,0.12mmol)的无水乙醚(18mL)溶液中加入2.5M正丁基锂的己烷溶液(0.1ml,0.27mmol)。在-78℃下滴加并在-78℃下再搅拌20分钟。向溶液中加入二辛基二氯硅烷(46mg,0.14mmol),将溶液升温至0℃室温并搅拌20小时。将溶液用乙醚(10mL)和水(20mL)萃取。将合并的有机层用MgSO4干燥。后在减压下除去溶剂,通过柱纯化残余物硅胶色谱(己烷),得到黄色油状物产物,产率35%。1H NMR(400MHz,CDCl3),δ7.84(s,1H),3.37(t,4H),0.41(s,9H)ppm。13C NMRδ:139.4,137.2,135.3,135.0,134.4,130.9,127.2,126.4,124.3,124.0,121.5,117.1ppm。MALDI-TOF MS:计算[M]:m/z=1670.9,测试[M]:m/z=1670.91。
实施例3化合物8合成
取化合物6(200mg,0.12mmol)置于100mL二口瓶,将二口瓶置换成氩气氛围,加入20mL无水四氢呋喃,用反应体系冷却到-78℃。在剧烈搅拌下向反应体系中滴加正丁基锂(0.91mmol,0.3 6mL,2.5M,正己烷溶液),反应混合物变为亮黄色溶液。半小时后,将反应混合物升温至0℃,再搅拌半小时。在剧烈搅拌下向反应混合物中滴加四氯化硅(10.2mg,0.06mmol)。在0℃下继续搅拌混合物,反应混合物变为褐色。一小时后向反应体系中加入10mL水淬灭反应。将反应混合物倒入100mL正己烷,用水洗有机相三次,每次用水100mL,用无水硫酸钠干燥有机相,过滤,收集滤液,旋转蒸发除去溶剂。用硅胶色谱柱分离纯化样品,用正己烷做淋洗剂,得到黄色固体产物,产率57%。1H NMR(400MHz,CDCl3),δ7.84(s,1H),3.37(t,4H),0.41(s,9H)ppm。13C NMRδ:139.4,137.2,135.3,135.0,134.4,130.9,127.2,126.4,124.3,124.0,121.5,117.1ppm。MALDI-TOF MS:计算[M]:m/z=2861.3,测试[M]:m/z=2861.32。
实施例4化合物9合成
在氩气氛下,向6(200mg,0.12mmol)的超干四氢呋喃(18mL)溶液中加入2.5M正丁基锂的己烷溶液(0.1mL,0.25mmol)。在-78℃下滴加并在-78℃下再搅拌20分钟。向溶液中加入三异丙基苯硼酸二甲酯(46.6mg,0.14mmol),将溶液升温至0℃室温并搅拌20小时。将溶液用二氯甲烷(10mL)和水(20mL)萃取。将合并的有机层用MgSO4干燥。后在减压下除去溶剂,通过柱纯化残余物硅胶色谱(正己烷),得到黄色油状物产物,产率40%。1H NMR(400MHz,CDCl3),δ7.93(s,2H),7.84(s,2H),3.62(s,2H),3.61(s,1H)3.37(t,8H),0.41(s,18H)ppm。13C NMRδ:147.9,147.8,139.4,137.2,135.3,135.0,134.5,134.4,131.3,127.2,126.4,124.0,123.0,122.3,121.5,117.1ppm。MALDI-TOF MS:计算[M]:m/z=1630.86,测试[M]:m/z=1630.5。
实施例5化合物10合成
化合物6(200mg,0.12mmol),Pd 2(dba)3(4.35mg,4mol%),NaOtBu(92.39mg,0.96mmol)和BINAP(10.1mg,0.0168mmol)的无水甲苯(2.5mL)溶液脱气20分钟。然后将辛胺(56.2mg,0.432mmol)加入到混合物中,在110℃和氩气氛下搅拌7小时。将水(20mL)加入到溶液中,并用乙醚(10mL×3)萃取溶液。将合并的有机层用MgSO4干燥。在减压下除去溶剂后,通过硅胶柱色谱(EA/己烷=1/50)纯化残余物,得到棕色固体产物,产率40%。1H NMR(400MHz,CDCl3),δ7.93(s,2H),4.90(t,2H),3.37(t,8H),1.62(q,15H),0.41(s,18H)ppm。13C NMRδ:139.4,137.2,135.3,135.0,134.4,131.3,130.9,127.2,126.7,126.4,126.0,124.3,124.0,121.5,117.1,58.9ppm。MALDI-TOF MS:计算[M]:m/z=1543.86,测试[M]:m/z=1543.81。
实施例6化合物11合成
在氩气氛下,将双(二苄基丙酮)钯(0)(6.92mg,0.012mmol,0.1当量)和dppf(9.32mg,0.0168mmol,0.14当量)溶解在5mL无水甲苯(催化剂溶液)中。向小瓶中加入化合物6(200mg,0.12mmol,1当量),硫代乙酸钾(13.7 2mg,0.168mmol,1.40当量)和磷酸钾(45.67mg,0.216mmol,1.80当量)。将小瓶抽空并充入氩气。连续加入0.5mL除氧的催化剂丙酮溶液。将混合物在130℃氩气下搅拌18小时。将混合物冷却至室温,加入2mL二乙醚。将混合物冷却至-30℃保持2小时,然后过滤。将残余物用冷乙醚、冷水/甲醇(1:1)和甲醇连续洗涤。通过从甲苯中重结晶得到进一步的纯化,得到灰白色固体产物,产率35%。1H NMR(400MHz,CDCl3),δ7.93(s,2H),3.37(t,8H),1.62(q,12H),0.41(s,18H)ppm。13C NMRδ:139.4,135.3,135.0,134.5,134.4,127.2,126.4,125.6,124.0,121.5,117.1ppm。MALDI-TOF MS:计算[M]:m/z=1448.64,测试[M]:m/z=1448.4。
实施例7化合物12合成
在氩气氛下向6(200mg,0.12mmol)的无水乙醚(50mL)溶液中,在-78℃下滴加2.5Mn-BuLi的己烷溶液(0.1,0.26mmol)并搅拌20分钟。将二甲基氨基甲酰氯的无水乙醚溶液(19.69mg,0.14mmol,在3mL乙醚中)加入溶液中,将溶液升温至0℃并搅拌1小时。将溶液用水淬灭并用乙醚(20mL×3)萃取。将合并的有机层用MgSO4干燥。减压除去溶剂后,将残余物溶于THF(35mL)中。通过硅胶柱色谱(EA/己烷=1/20)纯化残余物,得到红色固体产物,产率17%。1H NMR(400MHz,CDCl3),δ7.93(s,2H),3.37(t,8H),1.62(q,12H),0.41(s,18H)ppm。13C NMRδ:154.4,139.4,138.3,135.3,135.0,134.5,134.4,127.2,126.4,124.0,121.5,117.1ppm。MALDI-TOF MS:计算[M]:m/z=1448.64,测试[M]:m/z=1448.4。
实施例8化合物13合成
向12(65mg,0.045mmol)和丙二腈(8.93mg,0.135mmol)的乙醇(9mL)溶液中加入乙酸(1.3mL)和吡啶(1.3mL)。将溶液搅拌并回流5小时。将反应混合物冷却至室温。随后,滤出沉淀物并用乙醚洗涤,得到深绿色固体产物,产率25%。1H NMR(400MHz,CDCl3),δ7.93(s,2H),3.37(t,8H),1.62(q,12H),0.41(s,18H)ppm。13C NMRδ:160.1,139.4,136.9,135.3,135.0,134.5,134.4,130.9,127.2,126.4,124.0,121.5,117.1,113.6,92.1ppm。MALDI-TOFMS:计算[M]:m/z=1492.68,测试[M]:m/z=1492.8。
实施例9化合物14合成
向12(65mg,0.045mmol)的甲苯(9mL)溶液中加入劳森试剂(72.8mg,0.18mmol),将溶液110℃下搅拌并回流5小时。将反应混合物冷却至室温。随后,滤出沉淀物并用乙醚洗涤,得到黄色固体产物,产率7%。1H NMR(400MHz,CDCl3),δ7.93(s,2H),3.37(t,8H),1.62(q,12H),0.41(s,18H)ppm。13C NMRδ:144.4,139.4,136.9,135.3,135.0,134.5,130.9,127.2,126.4,124.0,121.5,117.1ppm。MALDI-TOFMS:计算[M]:m/z=2857.34,测试[M]:m/z=2857.5。
实施例10化合物15合成
将化合物6(200mg,0.12mmol)和双硼酸酯(148.68mg,0.24mmol)加入到100mL双口瓶中抽换气除净其中的氧气,迅速称取Pd(PPh3)4(19.81mg,0.012mmoL),将其在反应体系通氩气的情况下加入,迅速抽换气排尽体系中氧气。将2mol/L K2CO3溶液(0.6mL,1.2mmoL)、10mL THF分别氩气鼓泡30min后加入反应体系,90℃回流12小时。二氯甲烷萃取,饱和氯化钠溶液洗,无水硫酸钠干燥。柱层析淋洗剂使用石油醚。反应过程中溶液从淡黄色直到反应结束变为澄清棕色,得到黄色固体产物,产率24.5%。1H NMR(400MHz,CDCl3),δ7.93(s,2H),3.37(t,12H),1.62(q,18H),0.41(s,18H)ppm。13C NMRδ:139.4,135.3,134.5,134.4,131.7,127.2,126.4,125.7,124.3.9,121.5,117.1ppm。MALDI-TOF MS:计算[M]:m/z=1779.06,测试[M]:m/z=1779.1。
需要说明的是:通过TMS基团的卤代、LDA诱导氢迁移偶联反应和钯催化Suzuki偶联反应,合成更长的基于并噻吩的π共轭化合物,如下式所示:
可以看出,通过本发明制备的中间体合成具有单一分子量的π共轭化合物,方法相对单一,简单易行。合成的化合物大大的增加了分子的平面性和π-共轭体系电荷密度。
实施例11有机薄膜场效应晶体管器件制备和性能
有机薄膜场效应晶体器件包括衬底、栅极电极、介电层、有机层和源漏电极,结构如图2所示,器件按下述方法制备:
介电层制备:将沉积有栅极电极(高掺杂硅)和介电层(二氧化硅)的衬底(硅片)依次用去离子水、乙醇、丙酮超声清洗后烘箱烘干,待用。将5mg/mL的聚苯乙烯(重均分子量50kDa)氯仿溶液和5mg/mL的聚苯醚(重均分子量为50kDa)氯仿溶液按体积比1∶1的比例共混,搅拌15min左右,然后用匀胶机甩膜将混合溶液,以2000r/min的转速旋涂于介电层表面,放入烘箱,抽真空,真空度为0.1Pa,加热到80度处理1小时,自然冷却。聚合物层厚度为30nm。
有机层制备:将上述修饰的衬底放入真空镀膜机中,将真空度抽至为5×10-4Pa下,采用热蒸镀的方式,以0.8埃每秒的速度沉积有机物,至厚度为50nm形成有机层。
源漏电极制备;将金属掩模板有机层上,放入真空镀膜机中,将真空度抽至为5×10-4Pa下,然后加热蒸发源上的金,使其以1埃每秒的速度沉积到盖有掩模的有机薄膜上,形成厚度为40nm的金层作为源漏电极,得到有机场效应晶体管。
分别以并五苯(对比器件)和化合物14(器件1)作为有机物,分别在有机层制备中进行热蒸镀,形成有机层。
器件测试得出,器件1场效应器件迁移率达到2.2cm2/Vs,开关比为108;优于对比器件的迁移率0.31cm2/Vs,这主要是由于化合物14的两组11个芳香环或芳香杂环或芳香稠环单元以π-共轭相连的方式串联形成的共轭单元,在任何一个维度的平面上显示优异的平面性,同时,独特的空间正交结构,提供了更多维度的电荷传输通道,从而更有利于电荷在体相内的传输。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受实施例的限制,其它任何未背离本发明的精神实质与原理下所做的改变、修饰、组合、替代、简化均应为等效替换方式,都包含在本发明的保护范围之内。
Claims (5)
2.根据权利要求1所述的π-共轭化合物,其特征在于,所述化合物具有单一的分子量分布。
3.一种组合物,其特征在于,包含权利要求1所述的π-共轭化合物。
5.根据权利要求1所述的π-共轭化合物或权利要求3所述的组合物于制备有机电子器件中的应用。
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