CN103044661A - Arylene imide conjugated polymer and preparation method and application thereof to organic photoelectronic device - Google Patents
Arylene imide conjugated polymer and preparation method and application thereof to organic photoelectronic device Download PDFInfo
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- CN103044661A CN103044661A CN201110352509.9A CN201110352509A CN103044661A CN 103044661 A CN103044661 A CN 103044661A CN 201110352509 A CN201110352509 A CN 201110352509A CN 103044661 A CN103044661 A CN 103044661A
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- -1 Arylene imide Chemical class 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 120
- 239000000126 substance Substances 0.000 claims description 113
- 229910052757 nitrogen Inorganic materials 0.000 claims description 97
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- 239000002585 base Substances 0.000 claims description 30
- 230000003381 solubilizing effect Effects 0.000 claims description 25
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- 239000004793 Polystyrene Substances 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 21
- 229920002223 polystyrene Polymers 0.000 claims description 21
- 125000004429 atom Chemical group 0.000 claims description 20
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 17
- 230000005669 field effect Effects 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 230000026030 halogenation Effects 0.000 claims description 8
- 238000005658 halogenation reaction Methods 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000005401 electroluminescence Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011358 absorbing material Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- AIXAANGOTKPUOY-UHFFFAOYSA-N carbachol Chemical group [Cl-].C[N+](C)(C)CCOC(N)=O AIXAANGOTKPUOY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002240 furans Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 230000003252 repetitive effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 87
- 239000007787 solid Substances 0.000 description 43
- 238000005406 washing Methods 0.000 description 35
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 34
- 150000001721 carbon Chemical group 0.000 description 28
- 238000003756 stirring Methods 0.000 description 25
- 239000000460 chlorine Substances 0.000 description 24
- 239000007788 liquid Substances 0.000 description 23
- 238000001035 drying Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- 238000006392 deoxygenation reaction Methods 0.000 description 21
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- 238000005227 gel permeation chromatography Methods 0.000 description 18
- 238000000605 extraction Methods 0.000 description 17
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 17
- 238000004770 highest occupied molecular orbital Methods 0.000 description 16
- 229960001701 chloroform Drugs 0.000 description 15
- 239000004005 microsphere Substances 0.000 description 15
- 230000007717 exclusion Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 239000011324 bead Substances 0.000 description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 8
- 239000011368 organic material Substances 0.000 description 8
- 230000007704 transition Effects 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000003949 imides Chemical class 0.000 description 6
- 229930192474 thiophene Natural products 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical compound C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 description 5
- 238000010129 solution processing Methods 0.000 description 5
- 0 Cc1ccc(C=Cc2ccc(*)cc2C2=O)c2c1 Chemical compound Cc1ccc(C=Cc2ccc(*)cc2C2=O)c2c1 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002223 garnet Substances 0.000 description 4
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- TZIMDLZAZJJFSW-UHFFFAOYSA-N CC1(OB(OC1(C)C)SN(C1=CC=CC=C1)C1=CC=CC=C1)C Chemical compound CC1(OB(OC1(C)C)SN(C1=CC=CC=C1)C1=CC=CC=C1)C TZIMDLZAZJJFSW-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 3
- 150000003851 azoles Chemical class 0.000 description 3
- 125000005605 benzo group Chemical group 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 239000003444 phase transfer catalyst Substances 0.000 description 3
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical compound O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical group NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 2
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzo[h]quinoline Chemical compound C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 2
- RJCQBQGAPKAMLL-UHFFFAOYSA-N bromotrifluoromethane Chemical compound FC(F)(F)Br RJCQBQGAPKAMLL-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 239000010408 film Substances 0.000 description 2
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- LQERIDTXQFOHKA-UHFFFAOYSA-N nonadecane Chemical compound CCCCCCCCCCCCCCCCCCC LQERIDTXQFOHKA-UHFFFAOYSA-N 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 125000005561 phenanthryl group Chemical group 0.000 description 2
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical class C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- YCEZZDNWLVQCRU-UHFFFAOYSA-N 1,2-diaminoethyl Chemical group N[CH]CN YCEZZDNWLVQCRU-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- BSONECJEKLSHHH-UHFFFAOYSA-N 1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)fluoren-9-one Chemical compound CC1(C)OB(OC1(C)C)C1=CC=CC2=C1C(=O)C1=C2C=CC=C1 BSONECJEKLSHHH-UHFFFAOYSA-N 0.000 description 1
- LLAPDLPYIYKTGQ-UHFFFAOYSA-N 1-aminoethyl Chemical group C[CH]N LLAPDLPYIYKTGQ-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- 125000001478 1-chloroethyl group Chemical group [H]C([H])([H])C([H])(Cl)* 0.000 description 1
- 125000005978 1-naphthyloxy group Chemical group 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- MYKQKWIPLZEVOW-UHFFFAOYSA-N 11h-benzo[a]carbazole Chemical compound C1=CC2=CC=CC=C2C2=C1C1=CC=CC=C1N2 MYKQKWIPLZEVOW-UHFFFAOYSA-N 0.000 description 1
- UZGKAASZIMOAMU-UHFFFAOYSA-N 124177-85-1 Chemical compound NP(=O)=O UZGKAASZIMOAMU-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- JAAGHUBILRENEC-UHFFFAOYSA-N 1h-benzo[g]indazole Chemical compound C1=CC2=CC=CC=C2C2=C1C=NN2 JAAGHUBILRENEC-UHFFFAOYSA-N 0.000 description 1
- HIYWOHBEPVGIQN-UHFFFAOYSA-N 1h-benzo[g]indole Chemical compound C1=CC=CC2=C(NC=C3)C3=CC=C21 HIYWOHBEPVGIQN-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
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- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
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Abstract
The invention relates to an arylene imide conjugated polymer and a preparation method and application thereof to an organic photoelectronic device, wherein the arylene imide conjugated polymer 1 comprises one or more repetitive units R1 according with the formula I of -L-D-U-D-.
Description
Technical field
The present invention relates to based on the polymkeric substance of fragrant imide derivative and as the application of electron transport material in organic optoelectronic device such as organic field effect tube and polymer solar battery.
Background technology
The world today enters the information age, and information technology has been penetrated into each corner of national defence, industry, agricultural and people's daily life.Can say, information technology is one of crucial high-tech that is concerning national security, national economy and living standards of the people.In the tide of this field information technological revolution, the exploration of organic information material and device has become current in the world very active field with research.Realized obtaining, change, process and exporting of information with the device of organic materials preparation at present.Over nearly 10 years in the research of organic information material and device, organic/polymer photoelectron material and device (such as photodiode, field-effect transistor and solar cell etc.), particularly the research of organic polymer luminescent material and device is a dark horse, and most possibly obtains large-scale application.Although the principle of work of various devices is different, carrier transport is general, the crucial physical process of fundamental sum.Up to the present, the key issue of organic/polymer opto-electronic device development is high-level efficiency and long lifetime, and wherein the low mobility of organic semiconductor material is the bottleneck that solves these key issues.The carrier mobility of overwhelming majority organic materials is lower than 0.01cm
2V
-1s
-1Although the very high (＞10cm of the mobility of the monocrystal material such as pentacene and rubrene
2V
-1s
-1), but these monocrystalline still face a lot of problems in actual applications, such as cost and stability.([1]H.Sirringhaus，T.Kawase，R.H.Friend，T.Shimoda，M.Inbasekaran，W.Wu，E.P.Woo，“High-resolution inkjet printing of all-polymer transistor circuits”，Science，2000，290，2123.[2]B.Crone，A.Dodabalapur，Y.-Y.Lin，R.W.Filas，Z.Bao，A.LaDuca，R.Sarpeshkar，H.E.Katz，W.Li，“Large-scale complementary integrated circuits based on organic transistors”，Nature，2000，403，521.[3]M.Muccini，“A bright future for organic field-effect transistors”，Nature Mater.，2006，5，605.[4]A.R.Murphy，J.M.J.Frechet，“Organic semiconducting oligomers for use in thin film transistors”，Chem.Rev.，2007，107，1066.)。
N-type organic semiconductor material is extremely important to constructing p-n junction diode, bipolar transistor and complementary cmos circuit.Yet pi-conjugated organic molecule is the electron rich type mostly, is the p-type therefore.And n-type organic materials is relatively less, and the n-type organic materials of high electron mobility lacks more.Electron transport material commonly used has 8-hydroxyquinoline aluminum (Alq3), soccerballene (C
60), perylene diimide and cyano group phenylene ethylene (CN-PPV) etc.The mobility of overwhelming majority n-type organic semiconductor material is lower than 10
-4Cm
2V
-1s
-1The n-type organic molecule that electronic mobility is the highest will be counted soccerballene C
60He perylene diimide monocrystalline (＞1cm
2V
-1s
-1).But their weakness is responsive to water oxygen, so device property stable in the air is poor.And these monocrystalline face the problem of cost and stability in actual applications equally.([5]H.E.Katz，A.J.Lovinger，J.Johnson，C.Kloc，T.Siegrist，W.Li，Y.-Y.Lin，A.Dodabalapur，“A soluble and air-stable organic semiconductor with high electron mobility”，Nature，2000，404，478.[6]C.R.Newman，C.D.Frisbie，D.A.da Silva，J.L.Bredas，P.C.Ewbank，K.R.Mann，“Introduction to organic thin film transistors and design of n-channel organic semiconductors”，Chem.Mater.，2004，16，4436.[7]J.Zaumseil，H.Sirringhaus，“Electron and ambipolar transport in organic field-effect transistors”，Chem.Rev.，2007，107，1296.)
For real advantage such as easy processing and the low cost of organic materials in device application that realize, just must adopt solution processing technology such as silk screen printing and spray ink Printing etc.At present, the p-type organic materials mobility of solution processing reaches as high as＞1cm
2V
-1s
-1, and the n-type organic materials mobility of solution processing the highest＜1cm
2V
-1s
-1It is low and to problem ([8] L.L.Chua, J.Zaumseil, J.F.Chang such as water oxygen sensitivities that the n-type organic materials of solution processing still faces electronic mobility, E.C.W.Ou, P.K.H.Ho, H.Sirringhaus, R.H.Friend, " General observation of n-type field-effect behavior in organic semiconductors ", Nature, 2005,434,194.[9] Y.G.Wen, Y.Q.Liu, Adv.Mater., 2010,22,1331.).
Perylene diimide and naphthalimide are the fused ring compounds of a class electron deficiency, and Molecular interaction is stronger, have low lumo energy, and its small molecules monocrystalline electronic mobility of bibliographical information surpasses 1cm
2V
-1s
-1, the device electronic mobility of vacuum plating preparation surpasses 0.1cm
2V
-1s
-1, and the device electronic mobility of solution working method preparation generally is lower than 0.01cm
2V
-1s
-1We take the lead in reporting the synthetic and application in organic field effect tube of perylene diimide conjugated polymers, and Fa Xian perylene diimide polymkeric substance shows that high electron mobility (surpasses 0.01cm
2V
-1s
-1).The people such as Facchetti has reported that the naphthalimide conjugated polymers shows that also high electron mobility (surpasses 0.1cm subsequently
2V
-1s
-1) ([10] X.W.Zhan, Z.A.Tan, B.Domercq, Z.S.An, X.Zhang, S.Barlow, Y.F.Li, D.B.Zhu, B.Kippelen, S.R.Marder, J.Am.Chem.Soc., 2007,129,7246.[11] H.Yan, Z.H.Chen, Y.Zheng, C.Newman, J.R.Quinn, F.Dotz, M.Kastler, A.Facchetti, Nature, 2009,457,679.[12] J.E.Anthony, A.Facchetti, M.Heeney, S.R.Marder, X.W.Zhan, Adv.Mater., 2010,22,3876.).
Inventor of the present invention optimizes fragrant imide polymer from the angle of molecular engineering, as change copolymerization units character (neutral, give electronics and electron deficiency), substituting group (length, number and self-assembling function), on-link mode (OLM) (singly-bound, two key, triple bond) etc., thereby the raising electronic mobility is improved aerial stability.In addition, introducing main chain for electron conjugated group, be in order to utilize the transfer transport between electron deficiency imide derivative and the electron rich conjugation group, thereby absorbing a red shift to region of ultra-red, obtained like this black polymer that narrow band gap, wide band absorb.Use Suzuki, Stille, Sonagashira condensation route have prepared a series of new textures, the solution processibility is good, order is good, to air-stable, fragrant imide (conjugation) polymkeric substance that electronic mobility is high.Characterized the chemical structure of polymkeric substance with ultimate analysis, nucleus magnetic resonance, with gel permeation chromatography their molecular weight, tested the thermostability of polymkeric substance with thermogravimetric analysis and differential thermal analysis, characterized their electrochemical properties with cyclic voltammetric, studied the photophysical property of these polymkeric substance with ultra-violet absorption spectrum, made semiconductor layer with the polymkeric substance of preparation and prepared the n-slot field-effect transistor by the solution working method.Also with the polymkeric substance of preparation do electron acceptor(EA) and polymer-electronics to body blend constructed the all-polymer solar cell.Experimental result shows that these polymkeric substance are organic semiconductor material that are used for field-effect transistor and solar cell of high comprehensive performance.
Inventor of the present invention finds that the solution processibility of polymkeric substance of the present invention is good, is soluble in the organic solvents such as chloroform, tetrahydrofuran (THF) and chlorobenzene; Heat stability is good, for example initial heat decomposition temperature surpasses 400 ℃, and second-order transition temperature is above 200 ℃; Accept electronic capability strong, minimum not occupied orbital (LUMO) energy level is very low, for example is lower than-3.8eV; Electron-transporting is better, and for example electronic mobility surpasses 10
-2Cm
2/ V s.In addition, polymkeric substance light absorptive of the present invention is good, absorption region covering wide, narrow band gap.
Summary of the invention
The object of the present invention is to provide the polymkeric substance that contains the excellent sunlight capture ability of having of fragrant imide derivative and electron transport ability and as the application of electron transport material in organic field effect tube and solar cell.
The present invention relates to comprise the polymkeric substance that one or more meet the repeating unit R1 of general formula I:
-L-D-U-D-
Formula I
Wherein:
Many loop sections that U is comprised of 3 to 5 rings that are selected from 5-unit ring, 6-unit ring, 7-unit ring and composition thereof, other ring of at least one of in the ring of described many loop sections each and described many loop sections condenses, at least one ring of described many loop sections comprises at least one and forms electronics-accept atom of the part of group (electron-accepting group) Z, described many loop sections are optional by one or more solubilizing groups (solubilizing group) Y ' replacement
D is independently selected from, and in situation separately, does not exist, CH=CH, C ≡ C and its mixture;
L is general formula I I divalent group
Y is independently selected from, and in situation separately, is selected from hydrogen atom, unit price solubilizing group Y ' and its mixture;
Except following situation:
Polymkeric substance, it comprise be selected from following general formula I ' repeating unit, general formula I " the repeating unit R1* of repeating unit and composition thereof, as unique general formula I repeating unit R1:
Wherein, Y such as previous definition.
According to another embodiment of the present invention, polymkeric substance does not contain repeating unit R1*.
According to another embodiment of the present invention, polymkeric substance does not comprise a kind of polymkeric substance, and it comprises following general formula repeating unit R1**, as unique general formula I repeating unit R1
-L-D-U′″-D-
Formula I " '
Wherein:
Definition in L and D such as the above-mentioned content,
U " ' many loop sections of being formed by 3 to 5 rings that are selected from 5-unit ring, 6-unit ring, 7-unit ring and composition thereof; other ring of at least one of each in the ring of described many loop sections and described many loop sections condenses, and at least one ring of described many loop sections is furan nucleus
Described U " ' many loop sections are optional is replaced by one or more solubilizing groups Y '.
According to another embodiment of the present invention, polymkeric substance does not contain repeating unit R1**.
According to another embodiment of the present invention, D is C ≡ C.
According to another embodiment of the present invention, polymkeric substance D does not exist.
According to another embodiment of the present invention, polymkeric substance does not comprise a kind of polymkeric substance, and it comprises following general formula I " ' repeating unit R1***, as the general formula I repeating unit R1 of unique repeating unit
-L-U″″-
Formula I " "
Wherein:
Definition in L such as the above-mentioned content,
U " " be to be selected from following many loop sections
According to another embodiment of the present invention, polymkeric substance does not contain repeating unit R1***.
According to another embodiment of the present invention,
Be selected from Nai, perylene, guan and its mixture, and optional replaced by one or more unit price electron withdrawing groups X '.
According to another embodiment of the present invention, L is selected from general formula III divalent group, general formula I V divalent group, general formula V divalent group, general formula VI divalent group and composition thereof:
Wherein
Wherein:
M, m ', m ", m " ' representative from 0 to 2 integer;
X in situation separately, is independently selected from hydrogen atom, unit price electron withdrawing group X ' and its mixture;
Y independently, in situation separately, is selected from hydrogen atom, unit price solubilizing group Y ' and its mixture.
According to another embodiment of the present invention, L is the general formula III divalent group, m=0 wherein, such as general formula VII divalent group:
Wherein, Y ' in each situation, represents the solubilizing group of unit price.
According to another embodiment of the present invention, L is the mixture that comprises at least one general formula I V divalent group and at least one general formula V divalent group, m '=1 wherein, m wherein "=0; such as the mixture that is basically formed by general formula VIII divalent group, general formula I X divalent group, the further optional divalent group that comprises general formula X divalent group and/or general formula X I divalent group:
Wherein:
In each situation, X ' represents the electron withdrawing group of unit price, and Y ' represents the solubilizing group of unit price.
According to another embodiment of the present invention, the electron withdrawing group X ' of described unit price is independently from each other cyano group, C
1-C
60Acyl group, halogen, C
1-C
60Perhalogeno carbyl, C
1-C
60Partly halogenation alkyl and composition thereof, wherein C
1-C
60Partly the halogen atom and the hydrogen atom molar ratio that have of halogenation alkyl is at least 0.50.
According to another embodiment of the present invention, described polynuclear hydrocarbon part is not replaced by the electron withdrawing group of any unit price.
According to another embodiment of the present invention, the solubilizing group Y ' of described unit price is independently from each other C
1-C
60Alkyl, C
1-C
60Partly the halogenation alkyl, by one or more C
1-C
60Phenyl that oxygen base alkyl replaces and composition thereof, wherein C
1-C
60Partly the halogen atom and the hydrogen atom molar ratio that have of halogenation alkyl is at least 0.50.
According to another embodiment of the present invention, Y, in situation separately, the solubilizing group Y ' of unit price, its under 25 ℃ of temperature when being dissolved at least a solvent that is selected from chloroform, chlorobenzene and tetrahydrofuran (THF), it increases described structure adaptability degree at least 10% when being same as described polymkeric substance comparing with reference to the structure adaptability degree in the situation that described unit price solubilizing group Y ' is substituted by hydrogen atom.
According to another embodiment of the present invention, Y in each situation, is C2-C30 alkyl or by at least one C
2-C
30The phenyl that alkyl replaces.
According to another embodiment of the present invention, wherein U is selected from following radicals
Wherein:
A in each situation, represents the atom of VIA family independently;
E in each situation, represents E '-Y, VA family atom or its mixture independently;
E ' in each situation, represents IVA family atom independently, preferred C or Si;
Z is independently selected from, in situation separately,
Y is solubilizing group Y ' or its mixture of hydrogen atom, unit price, and wherein Y ' can define such as above-mentioned content, and Y can define such as above-mentioned content.
According to another embodiment of the present invention, U is selected from following radicals
According to another embodiment of the present invention, described at least one ring that comprises many loop sections of at least one atom that forms electronics-accept group is
Wherein Z such as above-mentioned content define.
According to another embodiment of the present invention, described at least one ring that comprises many loop sections of at least one atom that forms electronics-accept group is
Wherein Z such as above-mentioned content define.
According to another embodiment of the present invention, Z is
According to another embodiment of the present invention, Z is
According to another embodiment of the present invention, A represents sulphur atom.
According to another embodiment of the present invention, the A represention oxygen atom.
According to another embodiment of the present invention, at least one E represents VA family atom.
According to another embodiment of the present invention, at least one E represents nitrogen.
According to another embodiment of the present invention, at least two E, optional at least three E or at least four E represent VA family atom.
According to another embodiment of the present invention, the number (n of A
A), the number (n of the atom E of VA family
EV) and the number (n of Z
Z) summation
n
A+n
EV+n
Z
At least 4, preferably at least 5, more preferably at least 6.
According to another embodiment of the present invention, the number (n of A
A), the number (n of VA family atom
EY) summation
n
A+n
EV
At least 3, preferably at least 4.
According to another embodiment of the present invention, the number Z (n of Z
Z) be at least 2, preferably at least 3, more preferably at least 4.
According to another embodiment of the present invention, be repeating unit R1 greater than the repeating unit of 90 % by mole of %.
According to another embodiment of the present invention, basically all repeating units or even all repeating unit be repeating unit R1.
According to another embodiment of the present invention, the number-average degree of polymerization that polymkeric substance of the present invention has is at least 3, uses polystyrene to measure by GPC as calibration criterion.
According to another embodiment of the present invention, the number-average degree of polymerization that polymkeric substance of the present invention has is at the most 200, uses polystyrene to measure by GPC as calibration criterion.
According to another embodiment of the present invention, whole or whole repeating units is repeating unit R1 basically, and it meets one or more general formula X II
Wherein, Y ' in each situation, represents the solubilizing group of unit price, and it is described that preferred Y ' states content as defined above, and/or Y to state as defined above content described,
Such as general formula X III,
The number-average degree of polymerization that described polymkeric substance has is from 3 to 200, obtains as using the polystyrene calibration criterion to measure by GPC.
According to another embodiment of the present invention, polymkeric substance of the present invention is conjugated polymers.
The method for preparing the invention described above polymkeric substance, it comprises makes at least one general formula X IV Compound C 1:
Hal-L-Hal (XIV)
At least one Compound C 2 reaction with general formula X V:
V-U-V (XV)
Wherein:
Hal in situation separately, represents halogen atom, preferred bromine;
V in each situation, is
-C=C ,-C ≡ C and composition thereof,
That is, in the non-existent situation of D, V is
In the situation that D is-C=C that V is-C=C; In the situation that D is-C ≡ C that V is-C ≡ C; D be do not exist, CH=CH ,-situation of the mixing of C ≡ C under, V is
-C=C and-mixing of C ≡ C,
L and U have the implication identical according to foregoing respectively.
According to another embodiment of the present invention, in the presence of aromatic solvent such as toluene, described Compound C 1 and Compound C 2 reactions.
According to another embodiment of the present invention, so that described Compound C 1 and described Compound C 2 are at least 50 ℃ with react under 120 ℃ the temperature at the most.
According to another embodiment of the present invention, described Compound C 1 and described Compound C 2 are at catalyzer such as Pd (PPh
3)
4There is lower reaction.
According to another embodiment of the present invention, described Compound C 1 is reacted in the presence of alkali such as triethylamine with described Compound C 2.
The invention further relates to a kind of device, be selected from organic electro luminescence device, organic thermochromatic element, organic field effect tube and polymer solar battery, described device comprises according to the polymkeric substance of the invention described above or the polymkeric substance that prepared by the method according to the invention described above.
The invention still further relates to the polymkeric substance for preparing according to the polymkeric substance of the invention described above or by the method according to the invention described above and transmit application in the material as the light absorbing material in device and/or as electronics, wherein device is selected from organic electro luminescence device, organic thermochromatic element, organic field effect tube and polymer solar battery.
The example that is used for the aryl of polymkeric substance of the present invention includes but not limited to phenyl, naphthyl, anthryl, phenanthryl, naphthacenyl, pentacenyl, hexacenyl, pyrenyl, indenyl, xenyl, ortho-, meta-or p-tolyl, meta-tolyl, p-tolyl, p-tert-butyl-phenyl, p-(2-phenyl propyl) phenyl, 3-methyl-2-naphthyl, 4-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-anthryl, 4 '-methyl biphenyl, 4 "-tertiary butyl-p-terphenyl-4-base, 9; 9-dimethyl fluorene-1-base, 9,9-dimethyl fluorene-2-base; 9; 9-dimethyl fluorene-3-base, and 9,9-dimethyl fluorene-4-base.Other example comprises and belongs to phenyl, phenylene, and the substituting group of the binding substances of naphthyl and naphthylidene (such as phenyl napthyl, the naphthyl phenyl, the naphthyl naphthyl, naphthyl naphthyl naphthyl, phenyl naphthyl, naphthyl naphthyl phenyl, the naphthyl phenyl napthyl, the naphthyl phenyl, phenyl napthyl naphthyl, and phenyl napthyl phenyl).From replacement with 6-8 carbon atom or not to be substituted the group that aryl forms be preferred.Especially, phenyl, naphthyl and phenanthryl are preferred.
The example that is used for the alkyl of polymkeric substance of the present invention includes but not limited to methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, nonyl, decyl, the hendecane base, 12 carbon alkyl, the n-tridecane base, the n-tetradecane base, the pentadecane base, the hexadecane base, the heptadecane base, octadecyl, nonadecane base and petrosilane base, methylol, 1-hydroxyethyl, the 2-hydroxyethyl, 2-hydroxyl isobutyl-, 1,2-dihydroxy ethyl, 1,3-dihydroxyl sec.-propyl, 2,3-dihydroxyl-tertiary butyl, 1,2,3-trihydroxy-propyl group, chloromethyl, the 1-chloroethyl, 2-chloroethyl, 2-chlorine isobutyl-, 1, the 2-Dichloroethyl, 1,3-, two chloro isopropyls, 2, the 3-two chloro-tertiary butyls, 1,2,3-, three chloropropyls, brooethyl, 1-bromotrifluoromethane, 2-bromotrifluoromethane, 2-bromine isobutyl-, 1,2-, two bromotrifluoromethanes, 1,3-dibromo sec.-propyl, 2,3-, the two bromo-tertiary butyls, 1,2,3-three bromopropyls, an iodomethyl, 1-iodine ethyl, 2-iodine ethyl, 2-iodine isobutyl-, 1,2-diiodo-ethyl, 1,3-diiodo-sec.-propyl, 2,3-, the two iodo-tertiary butyls, 1,2,3-triiodo propyl group, one amino methyl, 1-amino-ethyl, 2-amino-ethyl, 2-aminoisobutyric base, 1,2-diamino ethyl, 1,3-diamino sec.-propyl, 2,3-diamino-tertiary butyl, 1,2,3-triamino propyl group, cyano methyl, 1-cyano ethyl, the 2-cyano ethyl, 2-cyano group isobutyl-, 1,2-dicyano ethyl, 1,3-dicyano sec.-propyl, 2,3-dicyano-tertiary butyl, 1,2,3-tricyano propyl group, the nitro methyl, the 1-nitro-ethyl, 2-nitro-ethyl, 2-nitro isobutyl-, 1,2-dinitrobenzene ethyl, 1,3-dinitrobenzene sec.-propyl, 2,3-dinitrobenzene-tertiary butyl, with 1,2,3-trinitro-propyl group.
The example that is used for the heterocyclic group of polymkeric substance of the present invention includes but not limited to thiophene, furans, pyrans, fen
Thiophene, pyrroles, imidazoles, pyrazoles, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, indoles, indazole, purine, quinolizine, quinoline, phthalazines, naphthyridines, quinoxaline, pteridine, carbazole, carboline, phenanthridines, phenanthroline, acridine, azophenlyene, thiazole, thiodiphenylamine,
Azoles, fen
Piperazine, two Thienopyrroles, three thiophthenes, benzo
The azoles base, benzimidazolyl-, thionaphthene, benzothiazolyl, thionaphthene, cumarone, chromene, benzo fen
Thiophene, benzopyrrole, benzoglyoxaline, benzopyrazoles, benzo pyridine, benzopyrazines, benzo pyrimidine, benzo pyridazine, benzo indolizine, benzindole, benzo indazole, benzo purine, benzoquinolizine, benzoquinoline, benzo phthalazines, benzo naphthyridines, Benzoquinoxalines, benzo pteridine, benzo carbazole, benzo carboline, benzo phenanthridines, benzo phenanthroline, benzacridine, phenonaphthazine, benzothiazole, benzo thiodiphenylamine, benzo
Azoles, benzo fen
The ring of the ring of piperazine or above-mentioned group and the ring of above-mentioned aryl, above-mentioned heterocyclic radical and/or the ring of above-mentioned heteroaryl condense derivative group, or the combination of above-mentioned group.In these substituting groups each can be substituted in addition.
The substituent example that further is substituted in each group in each polymkeric substance of the present invention comprises: alkyl (has preferred 1-30, more preferably 1-20, such as methyl, ethyl, sec.-propyl, the tertiary butyl, n-octyl, positive decyl, dodecyl, the n-tetradecane base, n-hexadecyl or Octadecane base); Cycloalkyl (have preferred 3-30, more preferably 3-20, or 3-10 carbon atom particularly preferably, such as cyclopropyl, cyclopentyl, or cyclohexyl); Alkenyl (have preferred 2-30, more preferably 2-20, or 2-10 carbon atom particularly preferably, such as vinyl, allyl group, crotyl, or 3-pentenyl); Alkynyl (have preferred 2-30, more preferably 2-20, or 2-10 carbon atom particularly preferably, such as propargyl or 3-pentynyl), aryl (have preferred 6-30, more preferably 6-20, or 6-12 carbon atom particularly preferably, such as phenyl, p-aminomethyl phenyl, naphthyl or anthryl); Amino (have preferred 0-30, more preferably 0-20, or 0-10 carbon atom particularly preferably, such as amino, methylamino, dimethylamino, diethylamino, dibenzyl amino, diphenyl amino, or xylyl amino); Alkoxyl group (have preferred 1-30, more preferably 1-20, or 1-10 carbon atom particularly preferably, such as methoxyl group, oxyethyl group, butoxy or 2-ethyl hexyl oxy); Aryloxy (have preferred 6-30, more preferably 6-20, or 6-12 carbon atom particularly preferably, such as phenyl oxygen base, 1-naphthyloxy, or 2-naphthyloxy); Heteroaryloxy (have preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, such as pyridyl oxygen base, pyrazoloxy, pyrimidyl oxygen base or quinolyl oxygen base); Acyl group (have preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, such as ethanoyl, benzoyl, formyl radical or valeryl); Alkoxy carbonyl (have preferred 2-30, more preferably 2-20, or 2-12 carbon atom particularly preferably, such as methoxycarbonyl or ethoxy carbonyl); Aryloxycarbonyl (have preferred 7-30, more preferably 7-20, or 7-12 carbon atom particularly preferably, such as phenyl oxygen base carbonyl); Acyloxy (have preferred 2-30, more preferably 2-20, or 2-10 carbon atom particularly preferably, such as acetoxyl group or benzoyloxy); Amide group (have preferred 2-30, more preferably 2-20, or 2-10 carbon atom particularly preferably, such as kharophen or benzoyl-amido); Alkoxycarbonyl amino (have preferred 2-30, more preferably 2-20, or 2-12 carbon atom particularly preferably, such as methoxycarbonyl amino); Aryloxy oxygen base amino (have preferred 7-30, more preferably 7-20, or 7-12 carbon atom particularly preferably, such as phenyl oxygen base carbonylamino); Sulfuryl amino (have preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, such as methane sulfonyl amido or benzenesulfonyl amino); Sulfamyl (have preferred 0-30, more preferably 0-20, or 0-12 carbon atom particularly preferably, such as amino-sulfonyl, methylamino alkylsulfonyl, dimethylamino-sulfonyl, or phenyl amino alkylsulfonyl); Formamyl (have preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, such as formamyl, methylamino formyl radical, diethylamino formyl radical, or phenyl amino formyl radical); Alkylthio (have preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, such as methylthio group or ethylmercapto group); Arylthio (have preferred 6-30, more preferably 6-20, or 6-12 carbon atom particularly preferably, such as thiophenyl); The heteroaryl sulfenyl (have preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, such as the pyridyl sulfenyl, 2-benzimidazolyl-sulfenyl, 2-benzo
Azoles base sulfenyl, or 2-[4-morpholinodithio base sulfenyl); Alkylsulfonyl (have preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, such as methylsulfonyl or tosyl group); Sulfinyl (have preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, such as methylsulfinyl or benzenesulfinyl); Urea groups (have preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, such as urea groups, methyl urea groups or phenyl urea groups); Phosphoamide base (have preferred 1-30, more preferably 1-20 or 1-12 carbon atom particularly preferably are such as diethyl phosphoamide or phenyl phosphamide); Hydroxyl; Sulfydryl; Halogen atom (such as fluorine atom, chlorine atom, bromine atoms, or iodine atom); Cyano group; Sulfo group; Carboxyl; Nitro; Hydroxamic acid group; Sulfino; Diazanyl; Imino-; Heterocyclic group (has preferred 1-30 or preferred 1-12 carbon atom and contain as heteroatomic for example nitrogen-atoms, Sauerstoffatom or sulphur atom, and specifically example comprises imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzo
The azoles base, benzimidazolyl-, and benzothiazolyl); And silyl (have preferred 3-40, more preferably 3-30, or 3-24 carbon atom particularly preferably, such as trimethyl silyl or triphenyl silyl).In these substituting groups each can be substituted in addition.
Description of drawings:
Fig. 1 is output and the transition curve that the embodiment of the invention 1 polymkeric substance ZXG-1-36 FET device is tested in air, electronic mobility μ
e=0.06cm
2V
-1s
-1Current on/off ratio I
On/ I
Off=10
5Threshold voltage V
Th=13V.
Fig. 2 is output and the transition curve that the embodiment of the invention 2 polymkeric substance ZXG-1-26 FET devices are tested in air, electronic mobility μ
e=0.02cm
2V
-1s
-1Current on/off ratio I
On/ I
Off=10
5Threshold voltage V
Th=-11V.
Fig. 3 is output and the transition curve that the embodiment of the invention 3 polymkeric substance ZXG-1-16 FET devices are tested in air, electronic mobility μ
e=7.6 * 10
-3Cm
2V
-1s
-1Current on/off ratio I
On/ I
Off=10
5Threshold voltage V
Th=22V.
Fig. 4 is output and the transition curve that the embodiment of the invention 4 polymkeric substance ZWY-2-7 FET devices are tested in nitrogen, electronic mobility μ
e=0.05cm
2V
-1s
-1Current on/off ratio I
On/ I
Off=10
4Threshold voltage V
Th=10V.
Fig. 5 is output and the transition curve that the embodiment of the invention 5 polymkeric substance ZWY-2-18 FET devices are tested under nitrogen, electronic mobility field-effect transistor I
DS/ (I
DS)
1/2-V
GSCurve of output μ
e=0.05cm
2V
-1s
-1Current on/off ratio I
On/ I
Off=10
5Threshold voltage V
Th=10V.
Fig. 6 is output and the transition curve that the embodiment of the invention 6 polymkeric substance ZWY-2-19 FET devices are tested in nitrogen, electronic mobility μ
e=0.02cm
2V
-1s
-1Current on/off ratio I
On/ I
Off=10
5Threshold voltage V
Th=14V.
Fig. 7 is the embodiment of the invention 7 polymkeric substance ZWY-1-54 cyclic voltammetry curves, highest occupied molecular orbital energy level HOMO=-5.7eV; Lowest unoccupied molecular orbital energy level LUMO=-3.8eV.
Fig. 8 is the embodiment of the invention 1 polymkeric substance ZXG-1-36 film ultraviolet-visible absorption spectroscopy, and the film absorption of this polymkeric substance can cover 300-900nm.
Fig. 9 is the current-voltage curve of the all-polymer solar cell device of the embodiment of the invention 1 polymkeric substance ZXG-1-36 and polythiofuran derivative blend preparation, and photovoltaic energy conversion efficient is 1.5%.
Embodiment
Following embodiment only is used for describing in detail the present invention, namely describes technical solution of the present invention in detail by synthetic example and sign embodiment, should not be understood to limit content of the present invention.
Poly-[N, N`-two (2-decyl tetradecyl)-3,4:9,10-perylene diimides-1,7-support]-replace-(2,6-diacetylene, three thiophthenes) (ZXG-1-36)
In 50mL round bottom there-necked flask, add N, N`-two (2-decyl tetradecyl)-1,7-two bromo-3,4:9,10-perylene diimide (0.2mmol, 244.7mg), and 2,6-diacetylene three thiophthenes (0.2mmol, 132.4mg), inflated with nitrogen deoxygenation 30 minutes.Under nitrogen protection, add Pd (PPh
3)
4(20 μ mol, 23m μ) and CuI (0.04mmol, 7.6mg), the inflated with nitrogen deoxygenation is 15 minutes again.Add dry toluene (10mL) and triethylamine (5mL), inflated with nitrogen deoxygenation 15 minutes is heated to 60 ℃ again.This dark red liquid becomes cyan thick liquid, cool to room temperature at 60 ℃ of lower stirring reactions after 3 days.Use CH
2Cl
2(2 * 100mL) extractions, and washing (2 * 100mL), anhydrous MgSO
4Dry.Be concentrated to 15mL, splash into 200mL methyl alcohol, filter, use washed with methanol, get blackish green solid.Then polymkeric substance is repeatedly crossed polystyrene microsphere (Bio-Rad Bio-Beads S-X1) exclusion volume chromatographic column on a small quantity, use tetrahydrofuran (THF) drip washing, desolventizing, drying gets blackish green solid (232mg, 89%).
1H NMR (400MHz, CDCl
3): δ 7.69 (br, 2H), 7.55 (br, 2H), 7.46 (br, 2H), 7.06 (br, 2H), 4.15 (br, 4H), 1.25 (br, 82H), 0.86 (br, 12H) .Anal.Calcd for (C
84H
106N
2O
4S
3)
n: C, 77.37; H, 8.19; N, 2.15.Found:C, 75.71; H, 8.03; N, 2.04.GPC:M
n=12335, M
w=14764, M
w/ M
n=1.20.UV (CHCl
3), λ
Max=453,680nm.HOMO=-5.7eV; LUMO=-4.0eV. μ
e=0.06cm
2V
-1s
-1I
On/ I
Off=10
5V
Th=13V (testing in the air).
Poly-[N, N`-two (2-decyl tetradecyl)-3,4:9,10-perylene diimides-1,7-support]-alternately-(4,4 '-dihexyl-2,2 '-Lian dithiazole-5,5 '-support) (ZXG-1-26)
In 25mL round bottom there-necked flask, add N, N`-two (2-decyl tetradecyl)-1,7-two bromo-3,4:9,10-perylene diimides (0.2mmol, 244.7mg), 5,5 '-two (tin trimethyl)-4,4 '-dihexyl-2,2 '-Lian dithiazole (0.2mmol, 132.4mg), and dry toluene (20mL), inflated with nitrogen deoxygenation 30 minutes.Add Pd (PPh under the nitrogen protection
3)
4(20 μ mol, 23mg), this yellow liquid was 110 ℃ of lower stirring reactions 3 days.In order to remove the bromine group on the polymer chain end, add 2-tributyl tin thiophene (11mg, 0.03mmol) reacted 10 hours, then add again the group that the tin trimethyl of the polymkeric substance end of the chain was removed in 2-bromothiophene (10mg, 0.06mmol) reaction in 10 hours.Then the garnet liquid cooling is to room temperature.Use CH
2Cl
2(2 * 100mL) extractions, and washing (2 * 100mL), anhydrous MgSO
4Dry.Be concentrated to 15mL, splash into 200mL methyl alcohol, filter, use washed with methanol, obtain the mulberry solid.Then with polymer filtration, repeatedly cross on a small quantity polystyrene microsphere (Bio-Rad Bio-Beads S-X1) exclusion volume chromatographic column, use trichloromethane drip washing, desolventizing, drying gets purple solid (270mg, 96%).
1H NMR (400MHz, CDCl
3): δ 8.73 (br, 2H), 8.36 (br, 4H), 4.14 (br, 4H), 2.62 (br, 4H), 2.02 (br, 2H), 1.62 (br, 4H), 1.25 (br, 92H), 0.84 (br, 18H) .GPC:M
n=4519, M
w=6520, M
w/ M
n=1.44.Anal.Calcd for (C
91H
132N
4O
4S
2)
n: C, 77.51; H, 9.43; N, 3.97.Found:C, 73.11; H, 9.05; N, 3.37%.UV (CHCl
3), λ
Max=349,481nm.HOMO=-6.1eV; LUMO=-3.9eV. μ
e=0.02cm
2V
-1s
-1I
On/ I
Off=10
5V
Th=-11V (testing in the air).
Poly-[N, N`-two (2-decyl tetradecyl)-3,4:9,10-perylene diimides-1,7-support]-replace-(9-Fluorenone-2,7-support) (ZXG-1-16)
In 25mL round bottom there-necked flask, add N, N '-two (2-decyl tetradecyl)-1,7-two bromo-3,4:9,10-perylene diimides (0.2mmol, 248mg), 2,7-two (4,4,5,5-tetramethyl--1,3,2-dioxaborolanyl)-9-Fluorenone (0.2mmol, 86mg), and K
2CO
3(1.2mmol, 166mg), inflated with nitrogen deoxygenation 30 minutes.Add Pd (PPh under the nitrogen protection
3)
4(6 μ mol, 6.9mg), toluene (5mL), phase-transfer catalyst Aliquat 336 (26.5mg) and deoxidation intermediate water (0.6mL) then are heated to 100 ℃, and keep stirring reaction three days, obtain dark red liquid.In order to remove the bromine group on the polymer chain end; (then (2.7mg) 100 ℃ of lower reactions 10 hours add the group that the tin trimethyl of the polymkeric substance end of the chain was removed in bromobenzene (0.1ml) reaction in 10 hours under nitrogen protection to add phenylo boric acid under the nitrogen protection.Then the garnet liquid cooling is to room temperature.Use CH
2Cl
2(2 * 100mL) extractions, and washing (2 * 100mL), anhydrous MgSO
4Dry.Be concentrated to 15mL, splash into 200mL methyl alcohol, filter, use washed with methanol, obtain the purple solid.Then with polymer filtration, repeatedly cross on a small quantity polystyrene microsphere (Bio-RadBio-Beads S-X1) exclusion volume chromatographic column, use trichloromethane drip washing, desolventizing, drying gets purple solid (221mg, 89%).
1H NMR (400MHz, CDCl
3): δ 8.73 (br, 2H), 8.47-7.52 (br, 10H), 4.13 (br, 4H), 2.01 (br, 2H), 1.22 (br, 80H), 0.84 (br, 12H) .GPC:M
n=8243, M
w=11405, M
w/ M
n=1.38.ANal.Calcdfor (C
85H
110N
2O
5)
n: C, 82.35; H, 8.94; N, 2.26.Found:C, 71.83; H, 8.81; N, 1.67%.UV (CHCl
3), λ
Max=562nm.HOMO=-6.0eV; LUMO=-3.9eV. μ
e=7.6 * 10
-3Cm
2V
-1s
-1I
On/ I
Off=10
5V
Th=22V (testing in the air).
(A) N, N`-two (2-decyl tetradecyl)-2,6-two bromo-Isosorbide-5-Nitraes, 5,8-benzene-naphthalene diimide
2,6-, two bromo-Isosorbide-5-Nitraes, 5,8-naphthalene tetracid acid anhydride (1.85mmol, 789mg), 2-decyl tetradecylamine (5.08mmol, 1.80g), o-Xylol (5mL), and propionic acid (3mL) is 140 ℃ of lower reaction overnight that stir.Behind the cool to room temperature, vacuum is revolved and is steamed desolventizing rear pillar Chromatographic purification [silicagel column, chloroform/sherwood oil (1: 1, v/v) drip washing] and obtain light yellow solid (270.5mg, 13.4%).
1HNMR (400MHz, CDCl
3): δ 8.99 (s, 2H), 4.14 (d, J=7.3Hz, 4H), 1.98 (m, 2H), 1.20-1.40 (m, 80H), 0.84-0.89 (m, 12H).
13C NMR (100MHz, CDCl
3): δ 161.3,161.1,139.3,128.5,127.9,125.4,124.2,45.6,36.6,32.1,32.0,31.7,30.2,29.8,29.7,29.5,26.5,22.8,14.3.MS (MALDI): m/z 1094.7 (M
+) .Anal.Calcd for C
62H
100Br
2N
2O
4: C, 67.86; H, 9.19; N, 2.55.Found:C, 67.73; H, 9.04; N, 2.59%.
(B) gather { [N, N`-two (2-decyl tetradecyl)-Isosorbide-5-Nitrae: 5,8-benzene-naphthalene diimide-2,6-support]-alternately-(10-hexyl-thiodiphenylamine-2,8-support) } (ZWY-2-7)
In 25mL round bottom there-necked flask, add N, N`-two (2-decyl tetradecyl)-2,6-two bromo-1,4:5,8-benzene-naphthalene diimide (0.15mmol, 166mg), 10-hexyl-2,8-two (4,4,5,5-tetramethyl--1,3,2-dioxaborolan-2-yl)-thiodiphenylamine (0.15mmol, 81mg), and K
2CO
3(0.95mmol, 131mg), inflated with nitrogen deoxygenation 30 minutes.Add Pd (PPh under the nitrogen protection
3)
4(31 μ mol, 35mg), toluene (4mL), and deoxidation intermediate water (0.5mL) are heated to 95 ℃.Yellow solution obtains sap green liquid 95 ℃ of lower stirring reactions three days.Add 95 ℃ of lower reactions of phenylo boric acid (8.1mg) 5 hours under the nitrogen protection, then add again bromobenzene (0.1ml) reaction 10 hours.Then the sap green liquid cooling is to room temperature.Use CH
2Cl
2(2 * 100mL) extractions, and washing (2 * 100mL), anhydrous MgSO
4Dry.Be concentrated to 15mL, splash into 200mL methyl alcohol, filter, use washed with methanol, obtain the sap green solid.Then with polymer filtration, repeatedly cross on a small quantity polystyrene microsphere (Bio-Rad Bio-Beads S-X1) exclusion volume chromatographic column, use trichloromethane drip washing, desolventizing, drying gets sap green solid (134mg, 73%).
1HNMR (400MHz, CDCl
3): δ 8.64 (br, 2H), 7.15-7.35 (br, 4H), 6.85-7.00 (br, 2H), (4.07 br, 4H), 3.99 (br, 2H), 1.97 (br, 4H), 1.05-1.60 (br, 86H), 0.80-1.00 (br, 15H) .GPC:M
n=7057, M
w=9577, M
w/ M
n=1.36.Anal.Calcd for (C
80H
119N
3O
4S)
n: C, 78.83; H, 9.84; N, 3.45.Found:C, 71.84; H, 9.42; N, 3.01%.UV (CHCl
3), λ
Max=361,632nm.HOMO=-5.8eV; LUMO=-3.7eV. μ
e=0.05cm
2V
-1s
-1I
On/ I
Off=10
4V
Th=10V (in nitrogen).
Poly-[N, N`-two (2-decyl tetradecyl)-3,4:9,10-perylene diimides-1,7-support]-replace-(10-hexyl-thiodiphenylamine-2,8-support) (ZWY-2-18)
In 50mL round bottom there-necked flask, add N, N`-two (2-decyl tetradecyl)-1,7-two bromo-3,4:9,10-perylene diimides (0.25mmol, 306mg), 10-hexyl-2,8-two (4,4,5,5-tetramethyl--1,3,2-dioxaborolan-2-yl)-thiodiphenylamine (0.25mmol, 135mg), the inflated with nitrogen deoxygenation is 30 minutes.Add Pd (PPh under the nitrogen protection
3)
4(10 μ mol, 11mg), toluene (6mL), phase-transfer catalyst Aliquat 336 (37 μ mol, 15mg) and deoxidation 2M K
2CO
3Solution (0.7mL).Dark red liquid heat to 95 ℃, and kept stirring reaction three days.Add phenylo boric acid (0.36mmol, 44mg) under the nitrogen protection, the black thick liquid then adds bromobenzene (0.9mmol, 0.1ml) reaction 10 hours again 95 ℃ of lower reactions 5 hours.Then black thick liquid cool to room temperature.Use CH
2Cl
2(2 * 100mL) extractions, and washing (2 * 100mL), anhydrous MgSO
4Dry.Be concentrated to 15mL, splash into 200mL methyl alcohol, filter, use washed with methanol, obtain black solid.Black solid is dissolved in 60mL CH
2Cl
2, then be added drop-wise to 500mL acetone, after then black solid being filtered, with acetone extracting 2 days in apparatus,Soxhlet's.Polymkeric substance behind the filtration drying is repeatedly crossed polystyrene microsphere (Bio-Rad Bio-BeadsS-X1) exclusion volume chromatographic column on a small quantity, uses trichloromethane drip washing, desolventizing, and drying gets black solid (181.3mg, 54%).
1H NMR (400MHz, CDCl
3): δ 8.6 (br, 2H), 8.3 (br, 4H), 7.8 (br, 2H), 7.5 (br, 4H), 4.1 (br, 6H), 2.00 (br, 4H), 1.2 (br, 86H), 0.8 (br, 15H) .GPC:M
n=7139, M
w=10401, M
w/ M
n=1.46.Anal.Calcd for (C
90H
123N
3O
4S)
n: C, 80.49; H, 9.23; N, 3.13.Found:C, 74.70; H, 8.82; N, 2.83%.UV (CHCl
3), λ
Max=329,518nm.HOMO=-5.6eV; LUMO=-3.7eV. μ
e=0.05cm
2V
-1s
-1I
On/ I
Off=10
5V
Th=10V (testing under the nitrogen).
Poly-[N, N`-two (2-hexyl decyl)-3,4:9,10-perylene diimides-1,7-support]-replace-(10-hexyl-thiodiphenylamine-2,8-support) (ZWY-2-19)
In 50mL round bottom there-necked flask, add N, N`-two (2-hexyl decyl)-1,7-two bromo-3,4:9,10-perylene diimides (0.25mmol, 251mg), 10-hexyl-2,8-two (4,4,5,5-tetramethyl--1,3,2-dioxaborolan-2-yl)-thiodiphenylamine (0.25mmol, 136mg), the inflated with nitrogen deoxygenation is 30 minutes.Add Pd (PPh under the nitrogen protection
3)
4(9 μ mol, 9mg), toluene (6mL), phase-transfer catalyst Aliquat 336 (94 μ mol, 38mg) and deoxidation 2M K
2CO
3Solution (0.7mL).Dark red liquid heat to 95 ℃, and kept stirring reaction three days.Add phenylo boric acid (0.24mmol, 29mg) under the nitrogen protection, the black thick liquid then adds bromobenzene (0.9mmol, 0.1ml) reaction 10 hours again 95 ℃ of lower reactions 5 hours.Then black thick liquid cool to room temperature.Use CH
2Cl
2(2 * 100mL) extractions, and washing (2 * 100mL), anhydrous MgSO
4Dry.Be concentrated to 15mL, splash into 200mL methyl alcohol, filter, use washed with methanol, obtain black solid.Black solid is dissolved in 60mL CH
2Cl
2, then be added drop-wise to 500mL acetone, after then black solid being filtered, with acetone extracting 2 days in apparatus,Soxhlet's.Polymkeric substance behind the filtration drying is repeatedly crossed polystyrene microsphere (Bio-Rad Bio-BeadsS-X1) exclusion volume chromatographic column on a small quantity, uses trichloromethane drip washing, desolventizing, and drying gets black solid (158.5mg, 57%).
1H NMR (400MHz, CDCl
3): δ 8.6 (br, 2H), 8.3 (br, 4H), 7.8 (br, 2H), 7.5 (br, 4H), 4.1 (br, 6H), 2.00 (br, 4H), 1.2 (br, 54H), 0.8 (br, 15H) .GPC:M
n=6694, M
w=8843, M
w/ M
n=1.32.Anal.Calcdfor (C
74H
91N
3O
4S)
n: C, 79.46; H, 8.20; N, 3.76.Found:C, 70.59; H, 8.43; N, 2.75%.UV (CHCl
3), λ
Max=329,518nm.HOMO=-5,6eV; LUMO=-3.7eV. μ
e=0.02cm
2V
-1s
-1I
On/ I
Off=10
5V
Th=14V (testing in the nitrogen).
(A) N, N`-two (2-2-hexyl decyl)-1,7-two bromo-3,4:9,10-perylene diimides
1,7-, two bromo-3,4:9,10-perylene tetracid acid anhydride (1.63g, 2.96mmol) joins 120mLBuOH/H
2O (1: 1, v/v) in, ultrasonic 10 minutes.2-hexyl decyl amine ((2.73g, 11.33mmol) joins in the above-mentioned mixed solution, this reaction solution under nitrogen protection 80 ℃ stirred 24 hours.Add dense HCl (13mL) behind the reaction solution cool to room temperature, stirred 30 minutes under the room temperature.With chloroform (2 * 90mL) extraction, the washing (2 * 180mL), anhydrous MgSO
4Dry.Rotary evaporation falls solvent, crosses silicagel column, uses CH
2Cl
2/ sherwood oil (1: 1) drip washing gets red solid (1.9g, 64%).
1H NMR (400MHz, CDCl
3): δ 9.36 (d, J=8.1Hz, 2H), 8.81 (s, 2H), 8.59 (d, J=8.2Hz, 2H), 4.12 (d, J=7.1Hz, 4H), 1.98 (m, 2H), 1.5-1.1 (m, 48H), 0.85 (m, 12H).
13C NMR (100MHz, CDCl
3): δ 163.0,162.5, and 138.0,132.9,132.6,129.8,129.0,128.3,126.8,123.0,122.6,120.8,44.8,36.6,32.0,31.8,31.6,30.0,29.7,29.6,29.3,26.5,22.6,14.1.MS (MALDI): m/z996 (M
+) .Anal.Calcd forC
56H
72Br
2N
2O
4: C, 67.46; H, 7.28; N, 2.81.Found:C, 67.53; H, 7.25; N, 2.91%.
(B) gather { [N, N`-two (2-hexyl decyl)-3,4:9,10-perylene diimides-1,7-support]-alternately-(three thiophthenes-2,6-support) } (ZWY-1-54)
In the 100mL there-necked flask, add N, N`-two (2-hexyl decyl)-1,7-two bromo-3,4:9,10-perylene diimides (415mg, 0.42mmol) and 2,6-two (tributyl tinbase) three thiophthene (325mg, 0.42mmol), add again dry toluene (20mL), inflated with nitrogen deoxygenation 30 minutes.Under nitrogen protection, add catalyst P d (PPh
3)
4(11mg, 10 μ mol) are heated to 110 ℃.This dark red solution becomes the dark solution of thickness, cool to room temperature after 2 days 110 ℃ of stirrings.The aqueous solution (10mL) that adds KF (5g) at room temperature stirs 2h and removes remaining tin.Then use CH
2Cl
2(2 * 150mL) extractions, and washing (2 * 300mL), anhydrous MgSO
4Dry.Be concentrated to 15mL, splash into 300mL methyl alcohol, filter, get black solid.Be dissolved in 60mL CH
2Cl
2, then be added drop-wise to 500mL acetone, after then black solid being filtered, with acetone extracting 2 days in apparatus,Soxhlet's.Polymkeric substance behind the filtration drying is repeatedly crossed polystyrene microsphere (Bio-Rad Bio-Beads S-X1) exclusion volume chromatographic column on a small quantity, uses trichloromethane drip washing, desolventizing, and drying gets black solid (405mg, 92%).
1H NMR (400MHz, CDCl
3): δ 8.7 (br, 2H), 8.3 (br, 4H), 7.6 (br, 2H), 4.1 (br, 4H), 2.0 (br, 2H), 1.2 (br, 48H), 0.8 (br, 12H) .Anal.Calcd for (C
64H
74N
2O
4S
3)
n: C, 74.52; H, 7.23; N, 2.72.Found:C, 71.84; H, 7.09; N, 2.61%.UV (CHCl
3), λ
Max=354,484,618nm.HOMO=-5.7eV; LUMO=-3.8eV. μ
e=4 * 10
-3Cm
2V
-1s
-1I
On/ I
Off=10
5V
Th=15V (testing in the nitrogen).
Poly-[N, N`-two (2-decyl tetradecyl)-3,4:9,10-perylene diimides-1,7-support]-alternately-(2,2 '-di-thiophene-5,5 '-support) (ZWY-1-56)
In the 100mL there-necked flask, add N, N`-two (2-decyl tetradecyl)-1,7-two bromo-3,4:9,10-perylene diimides (0.20mmol, 245mg) with 5,5 '-two (tributyl tin)-2,2 '-Lian two thiophene (0.20mmol, 150mg), add again dry toluene (20mL), inflated with nitrogen deoxygenation 30 minutes.Under nitrogen protection, add catalyst P d (PPh
3)
4(18 μ mol, 21mg) is heated to 90 ℃.This dark red solution becomes the dark solution of thickness, cool to room temperature after 3 days at 90 ℃ of stirring reactions.Add 90 ℃ of lower reactions of 2-tributyl tin thiophene (0.16mmol, 59mg) 5 hours under the nitrogen protection, add again 90 ℃ of lower reactions of 2-bromothiophene 10 hours under the nitrogen protection.Black thick liquid cool to room temperature.Then the aqueous solution (10mL) that adds KF (5g) at room temperature stirs 2h and removes remaining tin.Then use CH
2Cl
2(2 * 100mL) extractions, and washing (2 * 100mL), anhydrous MgSO
4Dry.Be concentrated to 5mL, splash into 200mL methyl alcohol, filter, wash with methyl alcohol, get black solid.Be dissolved in 60mL CH
2Cl
2, then be added drop-wise to 500mL acetone, after black solid is filtered, with acetone extracting 2 days in apparatus,Soxhlet's.Polymkeric substance behind the filtration drying is repeatedly crossed polystyrene microsphere (Bio-Rad Bio-Beads S-X1) exclusion volume chromatographic column on a small quantity, uses trichloromethane drip washing, desolventizing, and drying gets black solid (131mg, 53%).
1H NMR (400MHz, CDCl
3): δ 8.71 (br, 2H), 8.39 (br, 4H), 7.30 (br, 2H), (7.16 br, 2H), 4.14 (br, 4H), 2.00 (br, 2H), 1.60-1.00 (br, 80H), 0.95-0.80 (br, 12H) .Anal.Calcd for (C
80H
108N
2O
4S
2)
n: C, 78.38; H, 8.88; N, 2.29.Found:C, 75.05; H, 8.79; N, 2.20%.GPC:M
n=8876, M
w=15622, M
w/ M
n=1.76.HOMO=-5.7eV; LUMO=-3.8eV. μ
e=2 * 10
-4Cm
2V
-1s
-1I
On/ I
Off=10
3V
Th=35V (testing in the nitrogen).
(A) N, N` two (3,4,5-three (dodecyloxy) phenyl)-1,7-two bromo-3,4:9,10-perylene diimides
1,7-, two bromo-3,4:9,10-perylene tetracid acid anhydride (142mg, 0.26mmol) join in the 112mL propionic acid, ultrasonic 10 minutes.3,4,5-three (dodecyloxy) phenyl amine (540mg, 0.84mmol) joins in the above-mentioned mixed solution, this reaction solution 80 ℃ of stirring reactions 48 hours under nitrogen protection.The reaction solution cool to room temperature.With chloroform (2 * 150mL) extraction, the washing (2 * 150mL), anhydrous MgSO
4Dry.Rotary evaporation falls solvent, crosses silicagel column, uses CH
2Cl
2/ sherwood oil (3: 1) drip washing gets red solid (110mg, 24%).
1H NMR (400MHz, CDCl
3): δ 9.45 (d, J=8.2Hz, 2H), 8.91 (s, 2H), 8.68 (d, J=8.2Hz, 2H), (6.52 s, 4H), 4.04 (t, J=6.2Hz, 4H), 3.90 (t, J=6.2Hz, 8H), (1.85 m, 12H), 1.55-1.20 (m, 108H), (0.87 t, J=6.2Hz, 18H).
13C NMR (100MHz, CDCl
3): δ 162.6,162.0, and 153.6,138.5,137.9,132.2,129.6,129.2,128.5,128.1,126.5,123.0,122.6,121.2,106.7,73.4,68.9,31.9,30.6,29.929.8,29.7,29.5,29.4,29.3,26.2,26.1,22.7,14.1.MS (MALDI): m/z1807 (MH
+) .Anal.Calcd for C
108H
160Br
2N
2O
10: C, 71.82; H, 8.93; N, 1.55.Found:C, 71.38; H, 8.94; N, 1.64%.
(B) gather { [N, N '-two (3,4,5-three (dodecyloxy) phenyl)-3,4:9,10-perylene diimides-1,7-support]-alternately-(three thiophthenes-2,6-support) } (ZWY-1-48)
In the 100mL there-necked flask, add N, N '-two (3,4,5-three (dodecyloxy) phenyl)-1,7-two bromo-3,4:9,10-perylene diimides (722mg, 0.4mmol) and 2,6-two (tributyl tinbase) three thiophthene (310mg, 0.4mmol), add again dry toluene (20mL), inflated with nitrogen deoxygenation 30 minutes.Under nitrogen protection, add catalyst P d (PPh
3)
4(47mg, 40 μ mol) are heated to 110 ℃.This dark red solution becomes the dark solution of thickness, cool to room temperature after 2 days 110 ℃ of stirrings.The aqueous solution (10mL) that adds KF (5g) at room temperature stirs 2h and removes remaining tin.Then use CH
2Cl
2(2 * 150mL) extractions, and washing (2 * 300mL), anhydrous MgSO
4Dry.Be concentrated to 15mL, splash into 300mL methyl alcohol, filter, wash to get black solid with methyl alcohol.Be dissolved in 60mL CH
2Cl
2, then be added drop-wise to 500mL acetone, after then black solid being filtered, with acetone extracting 2 days in apparatus,Soxhlet's.Polymkeric substance behind the filtration drying is repeatedly crossed polystyrene microsphere (Bio-Rad Bio-Beads S-X1) exclusion volume chromatographic column on a small quantity, uses THF drip washing, desolventizing, and drying gets black solid (662mg, 90%).
1H NMR (400MHz, CDCl
3): δ 8.7 (br, 2H), 8.3 (br, 4H), 7.6 (br, 2H), 6.5 (br, 4H), 4.0 (br, 12H), 1.9-1.2 (br, 120H), 0.8 (br, 18H) .GPC:M
n, 2.5 * 10
4M
w, 3.8 * 10
4M
w/ M
n, 1.5.Anal.Calcd for (C
116H
162N
2O
10S
3)
n: C, 75.69; H, 8.87; N, 1.52.Found:C, 74.74; H, 8.54; N, 1.33%.UV (CHCl
3), λ
Max=357,485,620nm.HOMO=-5.9eV; LUMO=-3.7eV. μ
e=3 * 10
-4Cm
2V
-1s
-1I
On/ I
Off=10
3V
Th=4V (testing in the nitrogen).
Poly-[N, N`-two (3,4,5-three (dodecyloxy) phenyl)-3,4:9,10-perylene diimides-1,7-support]-replace-(2,6-diacetylene, three thiophthenes) (ZWY-1-59)
In 50mL round bottom there-necked flask, add N, N`-two (3,4,5-three (dodecyloxy) phenyl)-1,7-two bromo-3,4:9,10-perylene diimides (0.4mmol, 722.4mg), with 2,6-diacetylene three thiophthenes (0.4mmol, 97.6mg), inflated with nitrogen deoxygenation 15 minutes.Under nitrogen protection, add Pd (PPh
3)
4(40 μ mol, 46.3mg) and CuI (0.08mmol, 15.2mg), the inflated with nitrogen deoxygenation is 15 minutes again.Add dry toluene (20mL) and triethylamine (10mL), inflated with nitrogen deoxygenation 15 minutes is heated to 60 ℃ again. and this dark red liquid becomes cyan thick liquid, cool to room temperature at 60 ℃ of lower stirring reactions after 3 days.Use CH
2Cl
2(2 * 100mL) extractions, and washing (2 * 100mL), anhydrous MgSO
4Dry.Be concentrated to 15mL, splash into 200mL methyl alcohol, filter, use washed with methanol, get black solid.Be dissolved in 60mL CH
2Cl
2, then be added drop-wise to 500mL acetone, after then black solid being filtered, with acetone extracting 2 days in apparatus,Soxhlet's.Then polymkeric substance is repeatedly crossed polystyrene microsphere (Bio-RadBio-Beads S-X1) exclusion volume chromatographic column on a small quantity, use tetrahydrofuran (THF) drip washing, desolventizing, drying gets blackish green solid (680mg, 90%).
1H NMR (400MHz, CDCl
3): δ 8.68 (br, 6H), 7.45 (br, 2H), 7.06 (br, 4H), 4.06-3.87 (br, 12H), 1.20 (br, 120H), 0.83 (br, 18H) .GPC:M
n, 13838; M
w, 22439; M
w/ M
n, 1.62.Anal.Calcdfor (C
120H
162N
2O
10S
3)
n: C, 76.31; H, 8.65; N, 1.48.Found:C, 69.23; H, 8.37; N, 1.59%.UV (CHCl
3), λ
Max=422,675nm.HOMO=-5.7eV; LUMO=-4.2eV. μ
e=7 * 10
-5Cm
2V
-1s
-1I
On/ I
Off=10
3V
Th=14V (testing in the air).
Poly-[N, N` two (3,4,5-three (dodecyloxy) phenyl)-3,4:9,10-perylene diimide-1,7-support]-replace-(Isosorbide-5-Nitrae-diacetylene-benzene) (ZWY-1-61)
In 50mL round bottom there-necked flask, add N, N`-two (3,4,5-three (dodecyloxy) phenyl)-1,7-two bromo-3,4:9,10-perylene diimide (0.2mmol, 361.2mg), and Isosorbide-5-Nitrae-diacetylene-benzene (0.2mmol, 25.2mg), inflated with nitrogen deoxygenation 15 minutes.Under nitrogen protection, add Pd (PPh
3)
4(2 μ mol, 6mg) and CuI (0.04mmol, 10mg), the inflated with nitrogen deoxygenation is 15 minutes again.Add dry toluene (10mL) and triethylamine (5mL), inflated with nitrogen deoxygenation 15 minutes is heated to 60 ℃ again. and this atropurpureus liquid becomes the thick liquid of black, cool to room temperature after 3 days at 60 ℃ of lower stirring reactions.Use CH
2Cl
2(2 * 100mL) extractions, and washing (2 * 100mL), anhydrous MgSO
4Dry.Be concentrated to 15mL, splash into 200mL methyl alcohol, filter, use washed with methanol, get black solid.Be dissolved in again 60mL CH
2Cl
2, be added drop-wise to 500mL acetone, after then black solid being filtered, with acetone extracting 2 days in apparatus,Soxhlet's.Then polymkeric substance is repeatedly crossed polystyrene microsphere (Bio-Rad Bio-Beads S-X1) exclusion volume chromatographic column on a small quantity, use tetrahydrofuran (THF) drip washing, desolventizing, drying gets atropurpureus solid (320mg, 90%).
1H NMR (400MHz, CDCl
3): δ 8.62 (br, 6H), 7.90 (br, 2H), 7.70 (br, 2H), 6.99 (br, 4H), 4.05 (br, 12H), 1.20 (br, 120H), 0.83 (br, 18H) .GPC:M
n, 15226; M
w, 28568; M
w/ M
n, 1.87.Anal.Calcd for (C
118H
164N
2O
10)
n: C, 80.05; H, 9.34; N, 1.58.Found:C, 72.01; H, 8.89; N, 1.78%.UV (CHCl
3), λ
Max=378,562nm.HOMO=-6.0eV; LUMO=-4.2eV.
Poly-[N, N`-two (3,4,5-three (dodecyloxy) phenyl)-3,4:9,10-perylene diimide-1,7-support]-replace-acetylene (ZWY-1-63)
Add N in 50mL round bottom there-necked flask, N`-two (3,4,5-three (dodecyloxy) phenyl)-1,7-two bromo-3,4:9,10-perylene diimide (0.2mmol, 361mg), with 1,2-two (tributyl tin) acetylene (0.20mmol, 120.8mg), add again dry toluene (10mL), inflated with nitrogen deoxygenation 30 minutes.Under nitrogen protection, add catalyst P d (PPh
3)
4(20 μ mol, 24mg) is heated to 110 ℃.This dark red solution becomes the purple solution of thickness, cool to room temperature after 3 days at 110 ℃ of stirring reactions.The aqueous solution (10mL) that adds KF (5g) at room temperature stirs removed remaining tin in 2 hours.Then use CH
2Cl
2(2 * 100mL) extractions, and washing (2 * 100mL), anhydrous MgSO
4Dry.Be concentrated to 5mL, splash into 200mL methyl alcohol, filter, wash to get black solid with methyl alcohol.Be dissolved in 60mL CH
2Cl
2, be added drop-wise to 500mL acetone, after black solid is filtered, with acetone extracting 2 days in apparatus,Soxhlet's.Polymkeric substance behind the filtration drying is repeatedly crossed polystyrene microsphere (Bio-Rad Bio-Beads S-X1) exclusion volume chromatographic column on a small quantity, uses THF drip washing, desolventizing, and drying gets purple solid (152mg, 50%).
1H NMR (400MHz, CDCl
3): δ 8.98-7.53 (br, 6H), 6.49 (br, 4H), 4.02-3.95 (br, 12H), 1.20 (br, 120H), 0.83 (br, 18H) .GPC:M
n, 5653; M
w, 6308; M
w/ M
n, 1.12.Anal.Calcd for (C
110H
160N
2O
10)
n: C, 79.09; H, 9.65; N, 1.68.Found:C, 73.05; H, 8.34; N, 1.54%.UV (CHCl
3), λ
Max=544nm.
Embodiment 13
Poly-[N, N`-two (3,4,5-three (dodecyloxy) phenyl)-3,4:9,10-perylene diimides-1,7-support]-replace-(benzene-Isosorbide-5-Nitrae-support) (ZWY-1-65).
In 50mL round bottom there-necked flask, add N, N`-two (3,4,5-three (dodecyloxy) phenyl)-1,7-two bromo-3,4:9,10-perylene diimides (0.2mmol, 361.2mg), Isosorbide-5-Nitrae-to benzene hypoboric acid propylene glycol ester (0.2mmol, 49.2mg), deoxidation 2M K
2CO
3Solution (5mL) and THF (5mL), inflated with nitrogen deoxygenation 30 minutes.Add Pd (PPh under the nitrogen protection
3)
4(20 μ mol, 24mg) is heated to 70 ℃, and dark red liquid was 70 ℃ of stirring reactions three days, and system becomes purple thick liquid, cool to room temperature.Use CH
2Cl
2(2 * 50mL) extractions, and washing (2 * 50mL), anhydrous MgSO
4Dry.Be concentrated to 5mL, splash into 50mL methyl alcohol, filter, use washed with methanol, obtain black solid.Polymkeric substance behind the filtration drying is repeatedly crossed polystyrene microsphere (Bio-Rad Bio-Beads S-X1) exclusion volume chromatographic column on a small quantity, uses trichloromethane drip washing, desolventizing, and drying gets purple solid (160mg, 50%).
1H NMR (400MHz, CDCl
3): δ 8.69 (br, 6H), 7.18 (br, 2H), 7.01 (br, 2H), 6.47 (br, 4H), 4.03-3.95 (br, 12H), 1.20 (br, 120H), 0.83 (br, 18H) .GPC:M
n, 5080; M
w, 6838; M
w/ M
n, 1.35.Anal.Calcd for (C
114H
164N
2O
10)
n: C, 79.49; H, 9.60; N, 1.63.Found:C, 72.97; H, 8.99; N, 1.39%.UV (CHCl
3), λ
Max=548nm.
Poly-[N, N`-two (propyl group ethyl ether)-3,4:9,10-perylene diimides-1,7-support]-replace-(dodecyl two Thienopyrroles-2,6-support) (ZSM-1-10).
In the 100mL there-necked flask, add N, N`-two (propyl group ethyl ether)-1,7-two bromo-3,4:9,10-perylene diimides (216mg, 0.30mmol), dodecyl-2,6-tributyl tin-two Thienopyrroles (278mg, 0.30mmol) and dry toluene (10mL), stir.Logical nitrogen deoxygenation 30 minutes adds Pd (PPh under nitrogen protection
3)
4(40mg, 36 μ mol).Garnet liquid heat to 110 ℃, stirring reaction is three days under the nitrogen environment.Then black liquor is cooled to room temperature, the aqueous solution (10mL) that adds KF (5g) at room temperature stirs removed remaining tin in 2.5 hours.Use CHCl
3(2 * 150mL) extractions, and washing (2 * 300mL), anhydrous MgSO
4Dry.Be concentrated to 5mL, splash into 200mL methyl alcohol, filter, use washed with methanol, obtain black solid.Filtered in 2 days with acetone extracting in apparatus,Soxhlet's, then polymkeric substance is repeatedly crossed the polystyrene microsphere chromatographic column on a small quantity, use chloroform drip washing, desolventizing, drying gets black solid (249mg, 92%).
1H NMR (400MHz, CDCl
3): δ 8.7 (br, 2H), 8.3 (br, 4H), 7.4 (br, 2H), (4.5 br, 6H), 3.8 (br, 4H), 3.5 (br, 4H), (1.9 br, 2H), 1.7-1.2 (br, 22H), 0.8 (br, 9H) .GPC:M
n, 4.5 * 10
4M
w, 8.2 * 10
4M
w/ M
n, 1.8.Anal.Calcd for C
54H
55N
3O
6S
2: C, 71.57; H, 6.12; N, 4.64.Found:C, 69.16; H, 6.09; N, 4.32%.UV (CHCl
3), λ
Max=369,486,714nm.HOMO=-5.3eV; LUMO=-4.0eV. μ
e=4 * 10
-4Cm
2V
-1s
-1I
On/ I
Off=10
4V
Th=17V (in air). μ
h=4 * 10
-5Cm
2V
-1s
-1I
On/ I
Off=10
3V
Th=0V (testing in the air).
Embodiment 15
Poly-1,7-two (2 ,-three thiophthenes)-[N, N '-two (2-decyl-tetradecyl)-3,4:9,10-perylene diimides-6,6 '-support]-alternately-(dodecyl two Thienopyrroles-2,6-support) } (ZSM-1-12).
In the 100mL there-necked flask; add 1,7-two (6-bromo-three thiophthenes)-[N, N '-two (2-decyl-tetradecyl)-3; 4:9; 10-perylene diimides (403mg, 0.25mmol), dodecyl-2; 6-tributyl tin-two Thienopyrroles (232mg; 0.25mmol) and dry toluene (10mL), stir logical nitrogen deoxygenation 30 minutes, under nitrogen protection, add Pd (PPh
3)
4(22mg, 20 μ mol).Garnet liquid heat to 110 ℃, stirring reaction is three days under the nitrogen environment.Then reactant is cooled to room temperature, the aqueous solution (10mL) that adds KF (5g) at room temperature stirs removed remaining tin in 2.5 hours.Use CHCl
3(2 * 150mL) extractions, and washing (2 * 300mL), anhydrous MgSO
4Dry.Be concentrated to 5mL, splash into 200mL methyl alcohol, filter, use washed with methanol, obtain black solid.Then polymkeric substance is repeatedly crossed the polystyrene microsphere chromatographic column on a small quantity, use chloroform drip washing, desolventizing, drying gets black solid (428mg, 96%).
1H NMR (400MHz, CDCl
3): δ (ppm) 8.8 (br, 2H), 8.4 (br, 4H), 7.4 (br, 2H), 7.1 (br, 4H), 4.4-4.1 (br, 6H), 2.0 (br, 4H), 1.3 (br, 98H), 0.8 (br, 15H) .GPC:M
n, 9.4 * 10
3M
w, 1.6 * 10
4M
w/ M
n, 1.7.Anal.Calcd for C
108H
135N
3O
4S
8: C, 72.23; H, 7.58; N, 2.34.Found:C, 70.60; H, 7.53; N, 2.66%.UV (CHCl
3), λ
Max=492,770nm.HOMO=-5.4eV; LUMO=-3.8eV. μ
e=3 * 10
-4Cm
2V
-1s
-1I
On/ I
Off=10
3V
Th=27V (in nitrogen). μ
h=4 * 10
-5Cm
2V
-1s
-1I
On/ I
Off=10
3V
Th=-15V (testing in the air).
Embodiment 16
Electrochemical properties
Electrochemistry cyclic voltammetric (CV) experiment is finished at computer-controlled CHI660C voltammetric analyzer, adopts three-electrode system, polymkeric substance is coated on the platinum electrode as working electrode Ag/Ag
+Be reference electrode, platinum filament is that anhydrous acetonitrile is made solvent to electrode, (C
4H
9)
4NPF
6Be supporting electrolyte.Typical CV curve such as Fig. 7.
According to literature method (Pommerehne, J.; Vestweber, H.; Guss, W.; Mahrt, R.F.; Bassler, H.; Porsch, M.; Daub, J.Adv.Mater.1995,7,551), make HOMO and the lumo energy that benchmark can calculate polymkeric substance with ferrocene (FC).Minimum not occupied orbital (LUMO) energy level is very low, for example is lower than-3.8eV, accepts electronic capability strong; (3.9eV) suitable, so they are good electron acceptor materials with acceptor material PCBM best in the organic solar batteries.
Embodiment 17
The Preparation and characterization of field-effect transistor
Device adopts top contact structure.The polymkeric substance chloroformic solution of 10mg/mL is spun to forms organic semiconductor layer (100nm ± 10nm) in the silicon-dioxide substrate that OTS (octadecyltriethoxy silane) modifies.Be coated with 500nm SiO
2(electric capacity 7.5nF cm
-2) the n doped silicon wafer make grid, metal A u electrode (50nm) vacuum mask method evaporation to the polymer layer as source electrode and drain electrode.The wide W=3mm of raceway groove, long L=50 μ m.With Keithley 4200SCS semiconductor parameter determinator test component performance in nitrogen or air ambient.Part of devices output and transition curve such as Fig. 1-6), the field effect mobility is up to 10
-2Cm
2/ V s magnitude is one of amorphous polymer electronic mobility maximum of present solution processing, illustrates that this base polymer has good electronic transmission performance.
Embodiment 18
The all-polymer solar cell
Inventor of the present invention makes anode with transparent conductive glass ITO, aluminium stable in the air is made negative electrode, polymkeric substance ZXG-1-36 is electron acceptor(EA), and polythiofuran derivative is electron donor(ED), and their blend (1: 3) has prepared the all-polymer solar cell as photoactive layer.
Fig. 9 has provided the current-voltage curve of device, and device is in the situation that optimize not that (AM 1.5,100mW/cm at simulated solar irradiation
2) descend photovoltaic energy conversion efficient to reach 1.5%, suitable with the best all-polymer solar cell of bibliographical information, illustrate that this base polymer is desirable organic solar batteries electron acceptor material.
Claims (44)
1. comprise the polymkeric substance that one or more meet the repeating unit R1 of general formula I:
-L-D-U-D-
Formula I
Wherein:
Many loop sections that U is comprised of 3 to 5 rings that are selected from 5-unit ring, 6-unit ring, 7-unit ring and composition thereof, other ring of at least one of in the ring of described many loop sections each and described many loop sections condenses, at least one ring of described many loop sections comprises at least one and forms electronics-accept atom of the part of group Z, described many loop sections are optional by one or more solubilizing groups Y ' replacement
D is independently selected from, and in situation separately, does not exist, CH=CH, C ≡ C and its mixture;
L is general formula I I divalent group
Y in situation separately, is independently selected from hydrogen atom, unit price solubilizing group Y ' and its mixture;
Except following situation:
Polymkeric substance, it comprise be selected from following general formula I ' repeating unit, general formula I " the repeating unit R1* of repeating unit and composition thereof, as unique general formula I repeating unit R1:
Wherein, Y such as previous definition.
2. according to claim 1 polymkeric substance, it does not contain repeating unit R1*.
3. according to claim 1 and 2 polymkeric substance does not comprise a kind of polymkeric substance, and it comprises following general formula repeating unit R1**, as unique general formula I repeating unit R1
-L-D-U″′-D-
Formula I " '
Wherein:
Definition in L and D such as the claim 1,
U " ' many loop sections of being formed by 3 to 5 rings that are selected from 5-unit ring, 6-unit ring, 7-unit ring and composition thereof; other ring of at least one of each in the ring of described many loop sections and described many loop sections condenses, and at least one ring of described many loop sections is furan nucleus
Described U " ' many loop sections are optional is replaced by one or more solubilizing groups Y '.
4. according to claim 3 polymkeric substance, it does not contain repeating unit R1**.
5. according to each polymkeric substance of the claims, wherein D is C ≡ C.
6. according to each polymkeric substance of the claims 1-4, wherein D does not exist.
7. according to claim 6 polymkeric substance does not comprise a kind of polymkeric substance, and it comprises following general formula I " ' repeating unit R1***, as unique general formula I repeating unit R1
-L-U″″-
Formula I " "
Wherein:
Definition in L such as the claim 1,
U " " be to be selected from following many loop sections
Described many loop sections U " " optional replaced by one or more solubilizing groups Y '.
8. according to claim 7 polymkeric substance, it does not contain repeating unit R1***.
9. according to each polymkeric substance of the claims, wherein
Be selected from Nai, perylene, guan and its mixture, and optional replaced by one or more unit price electron withdrawing groups X '.
10. according to each polymkeric substance of the claims, wherein L is selected from general formula III divalent group, general formula I V divalent group, general formula V divalent group, general formula VI divalent group and composition thereof.
Wherein:
M, m ', m ", m " ' representative from 0 to 2 integer;
X in situation separately, is independently selected from hydrogen atom, unit price electron withdrawing group X ' and its mixture;
Y independently, in situation separately, is selected from hydrogen atom, unit price solubilizing group Y ' and its mixture.
11. polymkeric substance according to claim 10, wherein L is the general formula III divalent group, m=0 wherein, such as general formula VII divalent group:
Wherein, Y ' in each situation, represents the solubilizing group of unit price.
12. polymkeric substance according to claim 10, wherein L is the mixture that comprises at least one general formula I V divalent group and at least one general formula V divalent group, m '=1 wherein, m wherein "=0; such as the mixture that is basically formed by general formula VIII divalent group, general formula I X divalent group, the further optional divalent group that comprises general formula X divalent group and/or general formula X I divalent group:
Wherein:
In each situation, X ' represents the electron withdrawing group of unit price, and Y ' represents the solubilizing group of unit price.
13. according to each polymkeric substance in the claims, the electron withdrawing group X ' of wherein said unit price is independently from each other cyano group, C
1-C
60Acyl group, halogen, C
1-C
60Perhalogeno carbyl, C
1-C
60Partly halogenation alkyl and composition thereof, wherein C
1-C
60Partly the halogen atom and the hydrogen atom molar ratio that have of halogenation alkyl is at least 0.50.
14. according to each polymkeric substance among the claims 1-11, wherein said polynuclear hydrocarbon part is not replaced by the electron withdrawing group of any unit price.
15. according to each polymkeric substance in the claims, the solubilizing group Y ' of wherein said unit price is independently from each other C
1-C
60Alkyl, C
1-C
60Partly the halogenation alkyl, by one or more C
1-C
60Phenyl that oxygen base alkyl replaces and composition thereof, wherein C
1-C
60Partly the halogen atom and the hydrogen atom molar ratio that have of halogenation alkyl is at least 0.50.
16. according to each polymkeric substance of the claims, Y wherein, in situation separately, the solubilizing group Y ' of unit price, its under 25 ℃ of temperature when being dissolved at least a solvent that is selected from chloroform, chlorobenzene and tetrahydrofuran (THF), its with situation about being substituted by hydrogen atom except described unit price solubilizing group Y ' under when being same as the comparing with reference to the structure adaptability degree of described polymkeric substance, increase described structure adaptability degree at least 10%.
17. according to each polymkeric substance of the claims, wherein Y in each situation, is C
2-C
30Alkyl or by at least one C
2-C
30The phenyl that alkyl replaces.
18. according to each polymkeric substance of the claims, wherein U is selected from following radicals
Wherein:
A in each situation, represents the atom of VIA family independently;
E in each situation, represents E '-Y, VA family atom or its mixture independently;
E ' in each situation, represents IVA family atom independently, preferred C or Si;
Z is independently selected from, in situation separately,
Y is solubilizing group Y ' or its mixture of hydrogen atom, unit price, wherein Y ' can such as claim 15 definition, Y can be such as claim 16 and/or 17 definition.
19. according to the polymkeric substance of the claims 18, wherein U is selected from following radicals
And composition thereof.
20. according to each polymkeric substance of the claims, wherein said at least one ring that comprises many loop sections of at least one atom that forms electronics-accept group is
Or
Wherein Z such as claim 18 definition.
21. according to each polymkeric substance of the claims, wherein said at least one ring that comprises many loop sections of at least one atom that forms electronics-accept group is
Wherein Z such as claim 18 definition.
22. to 21 each polymkeric substance, wherein Z is according to claim 18
23. to 21 each polymkeric substance, wherein Z is according to claim 18
24. to 23 each polymkeric substance, wherein A represents sulphur atom according to claim 18.
25. according to claim 18 with 20 to 24 each polymkeric substance, wherein A represention oxygen atom.
26. to 25 each polymkeric substance, wherein at least one E represents VA family atom according to claim 18.
27. polymkeric substance according to claim 26, wherein at least one E represents nitrogen.
28. according to claim 26 or 27 polymkeric substance, at least two E wherein, optional at least three E or at least four E represent VA family atom.
29. according to claim 18 to 28 each polymkeric substance, the wherein number (n of A
A), the number (n of the atom E of VA family
EV) and the number (n of Z
Z) summation
n
A+n
EV+n
Z
At least 4, preferably at least 5, more preferably at least 6.
30. according to claim 18 to 29 each polymkeric substance, the wherein number (n of A
A), the number (n of VA family atom
EV) summation
n
A+n
EV
At least 3, preferably at least 4.
31. according to claim 18 to 30 each polymkeric substance, wherein the number Z (n of Z
Z) be at least 2, preferably at least 3, more preferably at least 4.
32. according to each polymkeric substance of the claims, be repeating unit R1 greater than the repeating unit of 90 % by mole of %.
33. polymkeric substance according to claim 32, wherein basically all repeating units or even all repeating unit be repeating unit R1.
34. according to each polymkeric substance of the claims, its number-average degree of polymerization that has is at least 3, uses polystyrene to measure by GPC as calibration criterion.
35. according to each polymkeric substance of the claims, its number-average degree of polymerization that has is at the most 200, uses polystyrene to measure by GPC as calibration criterion.
36. polymkeric substance according to claim 1, wherein whole or whole repeating unit is repeating unit R1 basically, and it meets one or more general formula X II
Wherein, Y ' in each situation, represents the solubilizing group of unit price, preferred Y ' definition as claimed in claim 15, and/or the definition of Y is as described in claim 16 and/or 17,
Such as general formula X III,
The number-average degree of polymerization that described polymkeric substance has is from 3 to 200, obtains as using the polystyrene calibration criterion to measure by GPC.
37. according to each polymkeric substance of the claims, it is conjugated polymers.
38. each the method for polymkeric substance of preparation the claims, it comprises makes at least one general formula X IV Compound C 1:
Hal-L-Hal (XIV)
At least one Compound C 2 reaction with general formula X V:
V-U-V (XV)
Wherein:
Hal in situation separately, represents halogen atom, preferred bromine; V in each situation, is
-C=C ,-C ≡ C and composition thereof, that is, in the non-existent situation of D, V is
In the situation that D is-C=C that V is-C=C; In the situation that D is-C ≡ C that V is-C ≡ C; D be do not exist, CH=CH ,-situation of the mixing of C ≡ C under, V is
-C=C and-mixing of C ≡ C,
L and U have respectively according to each identical implication of above-mentioned claim.
39. method according to claim 38, wherein, in the presence of aromatic solvent such as toluene, described Compound C 1 and Compound C 2 reactions.
40. according to claim 38 or 39 method, wherein so that described Compound C 1 and described Compound C 2 at least 50 ℃ with react under 120 ℃ the temperature at the most.
41. according to claim 38 to 40 each methods, wherein said Compound C 1 and described Compound C 2 are at catalyzer such as Pd (PPh
3)
4There is lower reaction.
42. according to claim 38 to 41 each methods, wherein said Compound C 1 is reacted in the presence of alkali such as triethylamine with described Compound C 2.
43. device, be selected from organic electro luminescence device, organic thermochromatic element, organic field effect tube and polymer solar battery, described device comprise according to claim 1 to 37 each polymkeric substance or by the polymkeric substance for preparing to 42 each methods according to claim 38.
44. according to claim 1 to 37 each polymkeric substance or by claim 38 to 42 each prepares polymkeric substance and transmits application in the material as light absorbing material in device and/or as electronics, wherein device is selected from organic electro luminescence device, organic thermochromatic element, organic field effect tube and polymer solar battery.
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| PCT/CN2012/001368 WO2013053204A1 (en) | 2011-10-11 | 2012-10-11 | Conjugated aramid polymer, preparation method for same, and application thereof in organic optoelectronic device |
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| WO2016026265A1 (en) * | 2014-08-21 | 2016-02-25 | Dow Global Technologies Llc | Polymeric charge transfer layer and organic electronic device containing the same |
| WO2016110140A1 (en) * | 2015-01-08 | 2016-07-14 | Dow Global Technologies Llc | Polymeric charge transfer layer and organic electronic device containing same |
| CN106229414A (en) * | 2016-09-21 | 2016-12-14 | 广西南宁荣威德新能源科技有限公司 | A kind of wide spectrum solar cell material |
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| US8796672B2 (en) * | 2008-02-05 | 2014-08-05 | Polyera Corporation | Perylene-imide semiconductor polymers |
| CN101407574B (en) * | 2008-12-01 | 2011-11-23 | 中国科学院长春应用化学研究所 | Donor-receptor type conjugated polymer containing dithiophen b pyrrole, preparation method and application thereof |
| CN101709109A (en) * | 2009-12-28 | 2010-05-19 | 大连理工大学 | Trapezoidal conjugated polymer and method for preparing same |
| CN102146153B (en) * | 2010-02-08 | 2013-01-16 | 海洋王照明科技股份有限公司 | Perylene tetracarboxylic diimide-carbazole-dithienyldiazosulfide conjugated polymer as well as preparation method and application thereof |
| CN102260369B (en) * | 2010-05-26 | 2013-01-16 | 海洋王照明科技股份有限公司 | Tetracarboxylic acid diimide copolymer containing cyclopentadienedithiophene unit, its preparation method and its application |
| CN102260370B (en) * | 2010-05-26 | 2013-01-16 | 海洋王照明科技股份有限公司 | Benzothiophene unit-containing perylene diimide copolymer, and preparation method and application thereof |
| CN102276804B (en) * | 2010-06-13 | 2013-04-17 | 海洋王照明科技股份有限公司 | Perylene tetracarboxylic diimide copolymer containing dithiophen-pyrrole unit and preparation method and application thereof |
| CN102286140B (en) * | 2010-06-18 | 2012-11-28 | 海洋王照明科技股份有限公司 | Perylene tetracarboxylic diimide copolymer containing dithieno quinoxaline unit as well as preparation method and application thereof |
| CN102295746B (en) * | 2010-06-25 | 2012-10-31 | 海洋王照明科技股份有限公司 | Thiophanthrene unit-containing perylene tetracarboxylic diimide copolymer and preparation method as well as application thereof |
| CN102295754B (en) * | 2010-06-28 | 2012-12-26 | 海洋王照明科技股份有限公司 | Naphthalene tetracarboxylic diimide-naphtho dithiophene-containing copolymer and preparation method as well as application thereof |
| CN102453236B (en) * | 2010-10-29 | 2013-08-07 | 海洋王照明科技股份有限公司 | Naphthalenetetracarboxylic acid diimide copolymer containing benzothiophene, and preparation method and application thereof |
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| WO2016026265A1 (en) * | 2014-08-21 | 2016-02-25 | Dow Global Technologies Llc | Polymeric charge transfer layer and organic electronic device containing the same |
| WO2016026266A1 (en) * | 2014-08-21 | 2016-02-25 | Dow Global Technologies Llc | Polymeric charge transfer layer and organic electronic device containing the same |
| CN106575718A (en) * | 2014-08-21 | 2017-04-19 | 陶氏环球技术有限责任公司 | Polymeric charge transfer layer and organic electronic device containing the same |
| US10454036B2 (en) | 2014-08-21 | 2019-10-22 | Dow Global Technologies Llc | Polymeric charge transfer layer and organic electronic device containing the same |
| WO2016110140A1 (en) * | 2015-01-08 | 2016-07-14 | Dow Global Technologies Llc | Polymeric charge transfer layer and organic electronic device containing same |
| CN106229414A (en) * | 2016-09-21 | 2016-12-14 | 广西南宁荣威德新能源科技有限公司 | A kind of wide spectrum solar cell material |
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