CN110003245A - A kind of alkyl/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2Type conjugated compound and the preparation method and application thereof - Google Patents
A kind of alkyl/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2Type conjugated compound and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110003245A CN110003245A CN201910279190.8A CN201910279190A CN110003245A CN 110003245 A CN110003245 A CN 110003245A CN 201910279190 A CN201910279190 A CN 201910279190A CN 110003245 A CN110003245 A CN 110003245A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- sulfanyl
- conjugated compound
- heteroaromatic rings
- type conjugated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 38
- 150000001875 compounds Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000006619 Stille reaction Methods 0.000 claims abstract description 6
- 150000003384 small molecules Chemical class 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 238000004440 column chromatography Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 claims description 4
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052714 tellurium Inorganic materials 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 238000010129 solution processing Methods 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims 2
- KBVDUUXRXJTAJC-UHFFFAOYSA-N 2,5-dibromothiophene Chemical compound BrC1=CC=C(Br)S1 KBVDUUXRXJTAJC-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 29
- 229930192474 thiophene Natural products 0.000 abstract description 17
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 239000000178 monomer Substances 0.000 abstract description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052794 bromium Inorganic materials 0.000 abstract description 2
- 239000002356 single layer Substances 0.000 abstract 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 abstract 1
- 230000021615 conjugation Effects 0.000 abstract 1
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 229910003472 fullerene Inorganic materials 0.000 abstract 1
- 230000003595 spectral effect Effects 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- -1 fluorine benzoxadiazole Chemical compound 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 239000010410 layer Substances 0.000 description 13
- 238000000862 absorption spectrum Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- OSDMWTCDUDJNGI-UHFFFAOYSA-N 2-octyl-1,3-thiazole Chemical compound CCCCCCCCC1=NC=CS1 OSDMWTCDUDJNGI-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- WIFCKLPZYYALGY-UHFFFAOYSA-N 1h-pyrrole-2,3-dione Chemical compound O=C1NC=CC1=O WIFCKLPZYYALGY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 125000003963 dichloro group Chemical group Cl* 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 3
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical compound SC1=NC=CS1 OCVLSHAVSIYKLI-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
- IFRTTXVMEUFUFK-UHFFFAOYSA-N N=1NN=C2C1C=CC=C2.[F] Chemical compound N=1NN=C2C1C=CC=C2.[F] IFRTTXVMEUFUFK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 description 2
- 150000002220 fluorenes Chemical class 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SLLFVLKNXABYGI-UHFFFAOYSA-N 1,2,3-benzoxadiazole Chemical compound C1=CC=C2ON=NC2=C1 SLLFVLKNXABYGI-UHFFFAOYSA-N 0.000 description 1
- ZWDFMOMBVDVEHE-UHFFFAOYSA-N 1,2-dicyclohexylethane-1,2-dione Chemical compound C1CCCCC1C(=O)C(=O)C1CCCCC1 ZWDFMOMBVDVEHE-UHFFFAOYSA-N 0.000 description 1
- PLLLVRSRXFDRHN-UHFFFAOYSA-N 1h-pyrazole;thiophene Chemical compound C=1C=CSC=1.C=1C=NNC=1 PLLLVRSRXFDRHN-UHFFFAOYSA-N 0.000 description 1
- RABBMOYULJIAFU-UHFFFAOYSA-N 1h-pyrrole;thiophene Chemical compound C=1C=CNC=1.C=1C=CSC=1 RABBMOYULJIAFU-UHFFFAOYSA-N 0.000 description 1
- HZWISIKLYWKROR-UHFFFAOYSA-N 1h-pyrrole;tin Chemical class [Sn].C=1C=CNC=1 HZWISIKLYWKROR-UHFFFAOYSA-N 0.000 description 1
- RXNZFHIEDZEUQM-UHFFFAOYSA-N 2-bromo-1,3-thiazole Chemical compound BrC1=NC=CS1 RXNZFHIEDZEUQM-UHFFFAOYSA-N 0.000 description 1
- IRTLROCMFSDSNF-UHFFFAOYSA-N 2-phenyl-1h-pyrrole Chemical compound C1=CNC(C=2C=CC=CC=2)=C1 IRTLROCMFSDSNF-UHFFFAOYSA-N 0.000 description 1
- RNXIRXYZZGOBQG-UHFFFAOYSA-N 2h-indeno[2,1-b]thiophene Chemical compound C1=CC=C2C3=CCSC3=CC2=C1 RNXIRXYZZGOBQG-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- CLEJZSNZYFJMKD-UHFFFAOYSA-N 3h-1,3-oxazole-2-thione Chemical compound SC1=NC=CO1 CLEJZSNZYFJMKD-UHFFFAOYSA-N 0.000 description 1
- ISADKOKKVZYYMM-UHFFFAOYSA-N 9h-carbazole;thiophene Chemical class C=1C=CSC=1.C1=CC=C2C3=CC=CC=C3NC2=C1 ISADKOKKVZYYMM-UHFFFAOYSA-N 0.000 description 1
- KGCPXLHLUMOWTK-UHFFFAOYSA-N 9h-fluorene;thiophene Chemical class C=1C=CSC=1.C1=CC=C2CC3=CC=CC=C3C2=C1 KGCPXLHLUMOWTK-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- BRUSMCPQIGBFIL-UHFFFAOYSA-N C1=CS(=O)C(=C1)F Chemical compound C1=CS(=O)C(=C1)F BRUSMCPQIGBFIL-UHFFFAOYSA-N 0.000 description 1
- ZTIJNCGRERWWOZ-UHFFFAOYSA-N CCCCCCCCC1=NC=C(C2=CC=C(C(C3=NC4=O)=C(CC(CC)CCCC)N=C3C4=O)S2)S1 Chemical compound CCCCCCCCC1=NC=C(C2=CC=C(C(C3=NC4=O)=C(CC(CC)CCCC)N=C3C4=O)S2)S1 ZTIJNCGRERWWOZ-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- ZZANWBXGYQVPCW-UHFFFAOYSA-N N1N=NC2=C1C=CC=C2.S2C=CC=C2 Chemical compound N1N=NC2=C1C=CC=C2.S2C=CC=C2 ZZANWBXGYQVPCW-UHFFFAOYSA-N 0.000 description 1
- SMCMWBCARVAUEA-UHFFFAOYSA-N N=1C(C(C=2C1C=CN2)=O)=O.S2C=NC=C2 Chemical compound N=1C(C(C=2C1C=CN2)=O)=O.S2C=NC=C2 SMCMWBCARVAUEA-UHFFFAOYSA-N 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- GZSVUKNENZZCDS-UHFFFAOYSA-N c1ccsc1.c1ccc2onnc2c1 Chemical class c1ccsc1.c1ccc2onnc2c1 GZSVUKNENZZCDS-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- BDDIUTHMWNWMRJ-UHFFFAOYSA-N octane;hydrobromide Chemical compound Br.CCCCCCCC BDDIUTHMWNWMRJ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000013087 polymer photovoltaic Methods 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- WEMNATFLVGEPEW-UHFFFAOYSA-N thiophene Chemical compound C=1C=CSC=1.C=1C=CSC=1 WEMNATFLVGEPEW-UHFFFAOYSA-N 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract
The invention belongs to organic photoelectrical material technical fields, and in particular to a kind of alkyl/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2Type conjugated compound and its preparation method and application.With the bis- thiophene donor monomers of fluoro- 2, the 2'- of 3,3'- bis- for center core, by bromine reaction on alkylated reaction, parental materials and stille coupling reaction, obtain D (A-Ar)2The conjugation small organic molecule photovoltaic donor material of type structure.D (A-Ar) according to the present invention2Type conjugated compound has good dissolubility and stability, has wide spectral absorption range, strong absorbing ability and suitable electrochemistry energy level, is expected to be used for the donor material of organic solar batteries.Its with fullerene PC71BM is that the ceiling capacity transformation efficiency of the single layer device bulk heterojunction solar cells of receptor and short circuit current are up to 8.91% and 16.75mA cm respectively‑2。
Description
Technical field
The invention belongs to organic photoelectrical material technical field, in particular to the D of a kind of alkyl/sulfanyl nitrogen heteroaromatic rings end
(A-Ar)2Type conjugated compound and the preparation method and application thereof.
Background technique
With the sharp increase and economic rapid development of population in the world, once fired as the fossil of important natural energy source
Material amount of storage is sharply reduced, in the near future will be depleted, and has excessively also been caused and can not have been reversed using fossil fuel
Environmental problem, the haze weather frequency of occurrences is higher and higher.In addition to water energy, wind energy, geothermal energy etc., solar energy is most important
Renewable energy, research shows that thousands of times that the energy of annual sunlight to the earth consumes gross energy more than the mankind at present, it is
It is inexhaustible.Biology in nature can convert solar energy into chemical energy by photosynthesis.And it is electric
The major impetus that can be leaped as scientific technological advance, national economy, plays indispensable role in human lives.Cause
This, the mankind urgently need to convert solar energy into electrical energy to substitute traditional energy.Early in the physicist of 19 th Century Frenchs
Becquerel finds that semiconductor can generate electromotive force when illuminated, and this phenomenon is physically being known as photogenic voltage
Effect (photovoltaic effect).1954, the Bell research institute in the U.S. successfully developed first block of silicon solar electricity
Pond, incident photon-to-electron conversion efficiency reach 6%, indicate that artificial device converts solar energy into electrical energy and become a reality.By in decades
Development, the solar battery technology of different materials is increasingly mature, and has their own characteristics each.Solar battery is according to material therefor
Difference can be divided into: silicon solar cell (silicon solar cells), inorganic salts solar battery (inorganic solar
Cells), dye-sensitized solar cells (dye sensitized solar cell, abbreviation DSSC), organic solar batteries
(organic solar cells, abbreviation OSCs) and perovskite solar battery (pervoskite solar cells) etc..Mesh
The preceding solar battery for realizing industrialization is mainly silicon solar cell, and highest transfer efficiency reaches under lab
26%, close to the upper limit of theoretical efficiency 29%.But since silicon single crystal processing technology is complicated, production solar battery is with high costs,
Energy consumption is high, hinders its further popularization.
Inorganic salts solar cell material such as GaAs, cadmium sulfide, copper indium selenide etc., photoelectric conversion efficiency is higher, material valence
Although lattice are expensive but cost is lower compared to monocrystalline silicon.However, the shortcomings that this kind of solar battery is that have severe toxicity, environment can be made
At serious pollution, and indium and selenium are all rarer elements, and source is restricted, these factors hinder its and practical answer
With.Dye-sensitized solar cells and perovskite solar battery preparation cost are lower, and photoelectric conversion efficiency is more satisfactory, especially
It is perovskite solar battery, efficiency is more than 20%.But they presently, there are easily cause pollution, device lifetime to environment
Short, the disadvantages of stability is low, more difficult progress flexible device preparation.The material source of organic solar batteries is extensive, low cost, divides
Sub- easy-regulating, light-weight, flexibility is good, can carry out the flexible preparation of large area.Therefore, organic solar batteries have long-range
The potentiality of development provide a kind of new selection to solve the energy problem in the following whole world.
So far, organic solar batteries mainly include body heterojunction organic solar batteries (BHJ-OSC) and dye
Expect sensitization solar battery (DSSC) two research directions.Wherein, body heterojunction organic solar batteries (BHJ-OSC) divide again
For polymer organic solar cell material (BHJ-PSC) and small molecule organic solar battery material (BHJ-SMOSC), it is based on
The photoelectric conversion peak efficiency (PCE) of polymer organic solar cell material (BHJ-PSC) Tandem devices has reached 17.3%,
The PCE of BHJ-SMOSC based on three component peak efficiency of small organic molecule has reached 13.6%, single layer device photoelectric conversion effect
Rate PCE has been up to 11.5%.Since BHJ-OSC is compared with DSSC, production technology is simpler, device is more stable, so
Obtain the favor of more and more researchers.Small organic molecule photovoltaic material, compared with Polymer photovoltaic materials, molecular structure with
Definitely and reliably, therefore, BHJ-SMOSC has very big development potentiality to relationship between device performance, has attracted more
Science, which is returned home, further studies and excavates.
The photoelectric conversion efficiency of organic small molecule material is also less than polymer material on the whole at present, and limited small molecule supplies
The design principle of body material seriously hinders the development of high efficiency organic molecule solar cell, how to pass through molecule knot
There is huge challenges for the small organic molecule photovoltaic material of the design acquisition efficient photoelectricity treater transfer efficiency of structure.This work not only mentions
The small molecule donor material of a kind of high performance organic solar batteries of novelty has been supplied, and has provided high efficiency small organic molecule
Material constructs mode and Research Thinking.
Summary of the invention:
The present invention provides a kind of alkyl/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2Type structure small organic molecule photovoltaic
The characteristics of material, such material is with the bis- thiophene donor monomers (D) of fluoro- 2, the 2'- of 3,3'- bis-, Diketopyrrolopyrrolederivative derivative
(A) be receptor unit (A), and respectively using 2- alkyl thiazole, 2- tin alkyl azoles, 2- sulfanyl thiazole or 2- sulfanyl tin azoles as
Terminal units (Ar).Construct D (A-Ar)2The linear small molecule photovoltaic donor material of structure, it is intended to realize it is wide absorb, it is strong absorb and
The macromolecular architecture of high mobility organic photovoltaic donor material is used for production small organic molecule photovoltaic device (OSCs), realizes
D (A-Ar)2The higher conversion efficiency of type structure photovoltaic material.
D(A-Ar)2Type conjugated compound structural formula is shown in Formulas I:
Wherein, A is to draw electronics bridge linkage group；D is center electron donating group；X=O, S, Se or Te；Y=O or S, R1Solely
Vertical is C6~C8Alkyl；
The characteristics of such material is using alkyl/miscellaneous condensed ring of sulfanyl virtue as terminal units.
Wherein, one of having structure can be selected in electrophilic bridge linkage group A, and R independently is C6~C12Alkyl；
It is described to have electron withdrawing properties bridging receptor A unit for diazosulfide, single fluorine diazosulfide, double fluorobenzene and thiophene
Diazole, double thiophene diazosulfides, double thiophene list fluorine diazosulfides, benzoxadiazole, single fluorine benzoxadiazole, double fluorobenzene are simultaneously
Oxadiazoles, double thiophene benzoxadiazoles, double thiophene list fluorine benzoxadiazoles, benzotriazole, single fluorine benzotriazole, double fluorobenzene
And triazole, double thiophene benzotriazole, double thiophene list fluorine benzotriazole, thiophene pyrrole and pyrroledione, thiazole pyrrolo-
Pyrroledione, pyridazole and pyrroledione, phenylpyrrole and pyrroledione, phenyl bioxindol, thienyl bioxindol, thiazolyl
Bioxindol, thiophene [3,4-b] the simultaneously fluoro- thiophene ester of -3-, thiophene [3,4-b] the simultaneously fluoro- thienone of -3-, thiophene [3,4-b] simultaneously -3-
Fluoro- thienone, thiophene [3,4-b] simultaneously -3- thienone, thiophene [3,4-b] and pyrroledione, double thiophene-thiophene [3,4-b] and pyrrole
Cough up diketone, double thiophene [4,5-b] and pyridone acene, double thiophene [3,4-b] and cyclohexyl diketone.
One of having structure can be selected in center electron donating group D, and R independently is C6~C12Alkyl；
D is functionalization condensed ring donor monomer, and the D conjugate unit is benzene, naphthalene, anthracene, phenanthrene, thiophene, alkyl bithiophene, alkyl
It is terthienyl, alkylthrophene bithiophene, triaryl amine, alkyl benzene thiophene, alkyl indacene, indeno thiophene, fluorenes, carbazole, double
Thiophene fluorenes, double thiophene carbazoles, benzo [b] thiazole silicon fluorene, tin alkyl pheno and two tin azoles of tin pheno, double tin pheno fluorenes and alkyl benzo [b].
The end miscellaneous condensed ring (Ar) of virtue is alkyl/sulfanyl functionalization condensed ring donor monomer, and one of having structure, R can be selected1
It independently is C6~C12Alkyl；
Ar is the miscellaneous condensed ring unit of virtue, the Ar conjugate unit be 2- alkylated oxazoline, 2- sulfanyl oxazole, 2- alkyl thiazole,
2- sulfanyl thiazole, 2- tin alkyl azoles, 2- sulfanyl tin azoles, 2- alkyl tellurium azoles and 2- sulfanyl tellurium azoles.
Above-mentioned D (A-Ar)2Type conjugated compound (small organic molecule photovoltaic material), preferably are as follows:
With 3,3'-, the bis- bis- thiophene of fluoro- 2,2'- (DFT) for electron donating group, Diketopyrrolopyrrolederivative derivative (TDPP) is
Drawing electron group, 2- octylthiazol (TZ) are the D (A-Ar) of terminal units2Type small molecule photovoltaic material DFT (TDPP-TZ)2。
Or with 3,3'-, the bis- bis- thiophene of fluoro- 2,2'- (DFT) for electron donating group, Diketopyrrolopyrrolederivative derivative (TDPP)
For drawing electron group, 2- sulphur octylthiazol (TZS) is the D (A-Ar) of terminal units2Type small molecule photovoltaic material DFT (TDPP-
TZS)2。
Based on alkyl/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2Type conjugated compound the preparation method comprises the following steps:
R will be had1Or SR1Nitrogen heteroaromatic rings (Ar) tin reagent and electrophilic bridge linkage group A unit (molar ratio be 2~3:1)
In Pd (PPh3)4Stille coupling reaction is carried out under (10%mol) catalytic condition in toluene solvant, is prepared corresponding one
Side is brominated, side compound containing alkyl/sulfanyl nitrogen heteroaromatic rings (Ar).
By acquired corresponding side, brominated, side (is rubbed containing alkyl/sulfanyl nitrogen heteroaromatic rings (Ar) with electron donating group D
You are than being 2~2.5:1) in Pd (PPh3)4Stille coupling reaction is carried out again in toluene solvant under (10%mol) catalytic condition,
Deoxidation treatment is carried out, heating reflux reaction 12 hours under nitrogen protection, obtaining containing alkyl/sulfanyl nitrogen heteroaromatic rings (Ar) is end
D (A-Ar)2Linear small molecule conjugated compound.A unit refers to one of electrophilic bridge linkage group described above, D
Unit refers to one kind of functionalization condensed ring donor monomer kind described above.
D (A-Ar) of the invention2The major advantage of type small molecule photovoltaic material is:
(1) synthesis based on alkyl/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2Type conjugated molecule has good molten
Xie Xing can be dissolved in most of organic solvent, such as methylene chloride, chloroform, tetrahydrofuran and chlorobenzene.
(2) due to the molecular structure of plane, synthesis based on alkyl/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2Type
Small molecule material carrier mobility with higher.
(3) synthesis based on alkyl/sulfanyl nitrogen heteroaromatic rings end conjugated molecule D (A-Ar)2With stronger molecule
Between interact, the effect of more close pi-pi accumulation.
(4) synthesis based on alkyl/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2To-receptor phase interaction in conjugated molecule
Presence forms stronger ICT effect, enhances charge transport properties.
(5) synthesis based on alkyl/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2Conjugated molecule, due to end alkyl and
The introducing of sulfanyl chain, can easily be accommodated dissolubility, and conjugated molecule is made to have better film forming.
(6) synthesis based on alkyl/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2Type conjugated molecule has suitable electricity
Chemical levels are suitable for electron donor material.
(7) synthesis based on alkyl/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2Type conjugated molecule is as electron acceptor
Material obtains higher energy conversion efficiency in organic solar batteries.
D (A-Ar) produced by the present invention2Type conjugated compound has high hole mobility, can be with PC71BM is blended, production
Small molecule photovoltaic device；Wherein, D (A-Ar)2Type conjugated compound and PC71It is 1:1 that mass ratio, which is blended, in BM.
Specifically: by D (A-Ar)2Type conjugated compound is applied to organic solar batteries as active layer, organic field is imitated
It answers in the devices such as transistor or organic electroluminescent LED.
The anode modification layer of the small molecule photovoltaic device is poly- ethylenedioxythiophene (PEDOT) coating.
The small organic molecule photovoltaic device includes indium tin oxide target Conducting Glass layer (ITO), anode layer, middle-jiao yang, function of the spleen and stomach
Pole decorative layer is poly- ethylenedioxythiophene (PEDOT, 30nm) coating；Cathode is the sedimentary of Ca (10nm)/Al (100nm)；It is living
Changing layer material is D of the present invention (A-Ar)2Molecule and PC71BM。
The thickness of the active layer is between 20 nanometers~1000 nanometers.
The active layer is realized by solution processing method, including spin coating, brushing, spraying, dip-coating, roller coating, screen printing
Brush, printing or inkjet printing methods, wherein solvent for use is organic solvent.
Detailed description of the invention
Fig. 1 is DFT of the present invention (TDPP-TZ)2Thermogravimetric curve figure.
Fig. 2 is DFT of the present invention (TDPP-TZ)2UV-visible absorption spectrum in dichloromethane solution.
Fig. 3 is DFT of the present invention (TDPP-TZ)2UV-visible absorption spectrum in solid film.
Fig. 4 is DFT of the present invention (TDPP-TZ)2Cyclic voltammetry curve figure on solid film.
Fig. 5 is DFT of the present invention (TDPP-TZ)2With PC71The mixed proportion of BM is that the J-V under 1:1 (w/w, 12mg/mL) is bent
Line chart.
Fig. 6 is DFT of the present invention (TDPP-TZ)2With PC71The mixed proportion of BM is EQE curve under 1:1 (w/w, 12mg/mL)
Figure.
Fig. 7 is DFT (TDPP-TZ)2With PC71The J of single-electron device when the mixed proportion of BM is 1:1 (w/w, 12mg/mL)1 /2- V curve.
Fig. 8 is DFT of the present invention (TDPP-TZS)2Thermogravimetric curve figure.
Fig. 9 is DFT of the present invention (TDPP-TZS)2UV-visible absorption spectrum in dichloromethane solution.
Figure 10 is DFT of the present invention (TDPP-TZS)2UV-visible absorption spectrum in solid film.
Figure 11 is DFT of the present invention (TDPP-TZS)2Cyclic voltammetry curve figure on solid film.
Figure 12 is DFT of the present invention (TDPP-TZS)2With PC71The mixed proportion of BM is the J-V under 1:1 (w/w, 12mg/mL)
Curve graph.
Figure 13 is DFT of the present invention (TDPP-TZS)2With PC71The mixed proportion of BM is that EQE is bent under 1:1 (w/w, 12mg/mL)
Line chart.
Figure 14 is DFT (TDPP-TZS)2With PC71The single-electron device when mixed proportion of BM is 1:1 (w/w, 12mg/mL)
J1/2- V curve.
Specific embodiment
Below by specific embodiment, the invention will be further described, but these specific embodiments are not in any way
It limits the scope of the invention.
Based on alkyl/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2The preparation route of type conjugated molecule is as follows,
Embodiment 1, compound 2- octylthiazol (TZR1) synthetic route it is as follows:
Under nitrogen protection, in 100mL there-necked flask, with dry ether dissolution 2- bromo thiazole (6.0g, 36.58mmol),
After 2.5M n-BuLi (16.0ml, 40.24mmol) is added dropwise at -78 DEG C, reacts two hours at -78 DEG C, it is added at one time bromine
For normal octane (7.0g, 36.58mmol), after insulation reaction half an hour, room temperature reaction is gone to overnight.Directly decompression is spin-dried for solvent,
Light yellow liquid is obtained, column chromatography for separation is carried out by eluant, eluent of petroleum ether, obtains product (TZR1) 6.0g, yield 84%.1H NMR
(500MHz,CDCl3) δ 7.66 (d, J=3.3Hz, 1H), 7.18 (d, J=3.3Hz, 1H), 3.05-2.97 (m, 2H), 1.79
(dt, J=15.4,7.6Hz, 2H), 1.33-1.26 (m, 11H), 0.87 (s, 3H)
Embodiment 2,2- octylthiazol -5- tributyl tin (SnTZR1) synthetic route it is as follows:
Under nitrogen protection, in 100mL there-necked flask, with dry tetrahydrofuran dissolution 2- octylthiazol (2.46g,
10.8mmol), after 2.5M n-BuLi (4.75ml, 11.88mmol) is added dropwise at -78 DEG C, reacts two hours at -78 DEG C, one
Tributyltin chloride (3.22ml, 11.88mmol) is added in secondary property, after insulation reaction half an hour, goes to room temperature reaction overnight.Directly
Decompression is spin-dried for solvent, obtains light yellow thick liquid (SnTZR1), it is directly used in and reacts in next step.1H NMR(400MHz,CDCl3)δ
7.58 (s, 1H), 3.06-3.03 (m, 2H), 1.80 (dt, J=15.0,7.4Hz, 2H), 1.58-1.51 (m, 6H), 1.46 (dt,
J=16.1,8.7Hz, 6H), 1.39-1.17 (m, 22H), 0.89 (t, J=7.2Hz, 12H)
Embodiment 3,3- (the bromo- 2- thienyl of 5-) -2,5- two (2- ethylhexyl) -6- (5- (2- octyl -5- thiazolyl) -
2- thienyl) pyrrolo-pyrrole-dione (BrTDPP-TZR1) synthetic route it is as follows:
Under nitrogen protection, in 100mL there-necked flask be added 20mL toluene, 2- octylthiazol -5- tributyl tin (286mg,
0.59mmol), 3,6- bis- (the bromo- 2- thienyl of 5-) -2,5- bis- (2- ethylhexyl)-pyrrolo-pyrrole-dione (400mg,
0.59mmol), tetra-triphenylphosphine palladium (34mg, 0.03mmol).It is heated with stirring to 80 DEG C under nitrogen atmosphere, stops after 4h anti-
It answers, is cooled to room temperature.Revolving removes solvent, adds alkane volume ratio to carry out for the mixed solution of 5:1 as eluant, eluent using petroleum ether/dichloro
Column chromatography for separation obtains product (BrTDPP-TZR1) 172mg, yield 30.0%.1H NMR(400MHz,CDCl3) δ 8.90 (d, J=
4.1Hz, 1H), 8.64 (d, J=4.2Hz, 1H), 7.84 (s, 1H), 7.27 (s, 1H), 7.23 (d, J=4.2Hz, 1H), 3.98
(dt, J=13.7,7.2Hz, 4H), 3.02 (t, J=7.7Hz, 2H), 1.82 (dt, J=15.3,7.6Hz, 4H), 1.32 (ddd,
J=25.4,15.9,8.4Hz, 34H), 0.94-0.86 (m, 15H)
Embodiment 4,2- sulphur octylthiazol (TZSR1) synthetic route it is as follows:
Under nitrogen protection and ice bath, in 100mL single port bottle be added 80mL dehydrated alcohol, potassium tert-butoxide (14.36g,
0.128mol) and 2- thiazole mercaptan (5g, 42.7mmol), after being stirred to react 30min, be slowly added to n-octane bromide (8.66g,
44.8mmol).After adding, back flow reaction 12h has reacted, water quenching is added to go out.Washing is extracted with ether (3 × 20mL), is merged organic
Layer simultaneously dries, filters to obtain filtrate with anhydrous magnesium sulfate, removes solvent, carries out column chromatography for separation by eluant, eluent of petroleum ether, must produce
Object (TZSR1) 9.06g, yield 92.4%.1H NMR(400MHz,CDCl3) δ 7.66 (d, J=3.4Hz, 1H), 7.20 (d, J=
3.4Hz, 1H), 3.30-3.15 (m, 2H), 1.75 (dt, J=15.0,7.4Hz, 2H), 1.51-1.36 (m, 2H), 1.33-1.15
(m, 9H), 0.88 (t, J=6.9Hz, 3H)
Embodiment 5,2- sulphur octylthiazol -5- tributyl tin (SnTZSR1) synthetic route it is as follows:
Under nitrogen protection, in 100mL there-necked flask, with the dry tetrahydrofuran dissolution pungent thiazole of 2- sulphur (2.0g,
8.90mmol), after 2.5M n-BuLi (3.92ml, 9.8mmol) is added dropwise at -78 DEG C, reacts two hours at -78 DEG C, once
Property be added tributyltin chloride (2.66ml, 9.8mmol), after insulation reaction half an hour, go to room temperature reaction overnight.Directly depressurize
It is spin-dried for solvent, obtains light yellow thick liquid (SnTZSR1), it is directly used in and reacts in next step.1H NMR(400MHz,CDCl3)δ7.57
(s, 1H), 7.26 (s, 1H), 3.30-3.05 (m, 3H), 1.76 (dt, J=15.0,7.4Hz, 3H), 1.58-1.48 (m, 6H),
1.45 (dt, J=16.1,8.7Hz, 5H), 1.39-1.18 (m, 22H), 0.89 (t, J=7.2Hz, 18H)
Embodiment 6,3- (the bromo- 2- thienyl of 5-) -2,5- two (2- ethylhexyl) -6- (5- (2- sulphur octyl -5- thiazole
Base) -2- thienyl) pyrrolo-pyrrole-dione (BrTDPP-TZSR1) synthetic route it is as follows:
Under nitrogen protection, in 100mL there-necked flask be added 20mL toluene, 2- sulphur octylthiazol -5- tributyl tin (213mg,
0.41mmol), 3,6- bis- (the bromo- 2- thienyl of 5-) -2,5- bis- (2- ethylhexyl)-pyrrolo-pyrrole-dione (280mg,
0.41mmol), tetra-triphenylphosphine palladium (7.12mg, 0.0062mmol).It is heated with stirring to 80 DEG C under nitrogen atmosphere, stops after 4h
Reaction, is cooled to room temperature.Revolving remove solvent, using petroleum ether/dichloro add alkane volume ratio for 5:1 mixed solution as eluant, eluent into
Row column chromatography for separation obtains product (BrTDPP-TZSR1) 172mg, yield 30.0%.1H NMR(300MHz,CDCl3)δ8.89(d,
J=4.2Hz, 1H), 8.64 (d, J=4.1Hz, 1H), 7.80 (s, 1H), 7.22 (dd, J=4.2,1.7Hz, 2H), 3.97 (dd,
J=12.7,7.6Hz, 4H), 3.29-3.18 (m, 2H), 1.84 (dd, J=11.8,7.2Hz, 2H), 1.81-1.68 (m, 2H),
1.30 (d, J=14.3Hz, 30H), 0.89-0.79 (m, 15H)
Embodiment 7, target compound FBT (TDPP-TZR1)2Synthetic route it is as follows:
Under nitrogen protection, 10mL toluene, 3- (the bromo- 2- thienyl of 5-) (2- second of -2,5- bis- are added in 100mL single port bottle
Base hexyl) -6- (5- (2- octyl -5- thiazolyl) -2- thienyl) pyrrolo-pyrrole-dione (126mg, 0.157mmol), (3,
Fluoro- [2,2'- bis- thiophene] -5,5'-, the bis--tributyl tin (42mg, 0.078mmol) of 3'- bis-, tetra-triphenylphosphine palladium (5.46mg,
0.0048mmol).It is heated with stirring to 110 DEG C under nitrogen atmosphere, stops reaction after 12h, is cooled to room temperature.Revolving removes molten
Agent adds alkane volume ratio to carry out column chromatography for separation as eluant, eluent for the mixed solution of 2:1, obtains product FBT using petroleum ether/dichloro
(TDPP-TZR1)2160mg, yield 72.0%.1H NMR(400MHz,CDCl3) δ 8.93 (d, J=4.3Hz, 2H), 7.75 (s,
1H), 7.22 (s, 1H), 7.15 (s, 1H), 6.99 (s, 1H), 3.98 (s, 4H), 2.91 (t, J=7.1Hz, 2H), 1.88 (s,
2H), 1.75 (s, 2H), 1.31 (d, J=47.2Hz, 60H), 0.93-0.86 (m, 30H)
Embodiment 8, target compound FBT (TDPP-TZSR1)2Synthetic route it is as follows:
Under nitrogen protection, 10mL toluene, 3- (the bromo- 2- thienyl of 5-) (2- second of -2,5- bis- are added in 100mL single port bottle
Base hexyl) -6- (5- (2- sulphur octyl -5- thiazolyl) -2- thienyl) pyrrolo-pyrrole-dione (150mg, 0.18mmol), (3,
Fluoro- [2,2'- bis- thiophene] -5,5'-, the bis--tributyl tin (48mg, 0.09mmol) of 3'- bis-, tetra-triphenylphosphine palladium (6.3mg,
0.0054mmol).It is heated with stirring to 110 DEG C under nitrogen atmosphere, stops reaction after 12h, is cooled to room temperature.Revolving removes molten
Agent adds alkane volume ratio to carry out column chromatography for separation as eluant, eluent for the mixed solution of 2:1, obtains product FBT using petroleum ether/dichloro
(TDPP-TZSR1)2160mg, yield 72.0%.1H NMR(400MHz,CDCl3)δ8.96–8.90(m,2H),7.67(s,1H),
7.12 (s, 1H), 7.03 (d, J=4.0Hz, 1H), 6.89 (s, 1H), 3.93 (d, J=13.3Hz, 4H), 3.11 (t, J=
7.3Hz, 2H), 1.87 (s, 2H), 1.73-1.65 (m, 2H), 1.32 (dd, J=38.3,7.0Hz, 60H), 0.93 (ddd, J=
19.8,18.9,6.3Hz,30H).
Embodiment 9
D(A-Ar)2The production of the performance characterization and its photovoltaic optical device of type small molecule photovoltaic material and the survey of luminescent properties
Examination.
D(A-Ar)2Type small molecule photovoltaic material1H NMR spectra is purple by Bruker Dex-400NMR Instrument measuring
Outside-visible absorption spectra is measured by HP-8453 ultraviolet-visible spectrometer, and fluorescence spectrum passes through HITACHI-850 fluorescence spectrum
Instrument measurement.
Based on D (A-Ar)2The photovoltaic device of type small molecule material includes: indium tin oxide target (ITO) electro-conductive glass anode layer, gathers
Ethylenedioxythiophene (PEDOT) anode modification layer.Activation is layer by layer by the small molecule material and PC71BM, which is blended, to be constituted, and is blended
Than being classified as 1:1.Cathode is made of Ca (10nm)/Al (100nm) layer.
Embodiment 10
DFT(TDPP-TZ)2Photophysics and its small molecule photovoltaic device performance
DFT(TDPP-TZ)2Thermogravimetric curve figure it is as shown in Figure 1.Its decomposition temperature is 378 DEG C.
DFT(TDPP-TZ)2In CHCl3Ultra-violet absorption spectrum in solution is as shown in Figure 2；Wherein the absorption peak of 363nm is
π-π * transition absorption the peak of the small molecule material, the absorption peak of 650nm are the electricity that donor monomer (DFT) arrives receptor unit (DPP)
Lotus shifts (ICT) transition absorption peak.
DFT(TDPP-TZ)2Ultra-violet absorption spectrum in solid film is as shown in Figure 3.Wherein the figure of absorption spectrum is substantially
It is identical, but absorption peak has different degrees of red shift, this is because in solid film caused by pi-pi accumulation.Peak position calculates by
The band gap of the material is 1.56eV.
DFT(TDPP-TZ)2Cyclic voltammetry curve in solid film is as shown in Figure 4.It shows two groups of reversible oxidations
Peak can be attributed to the oxidation peak of donor monomer DFT and receptor unit DPP respectively.Thus obtain the material HOMO energy level be-
5.41eV。
DFT(TDPP-TZ)2With PC71The mixed proportion of BM is J-V curve graph such as Fig. 5 institute under 1:1 (w/w, 12mg/mL)
Show；Under this condition, the short circuit current of device is 16.12mA/cm2, open-circuit voltage 0.75V, fill factor 63.09%,
Photovoltaic efficiency is 7.63%.
DFT(TDPP-TZ)2With PC71The mixed proportion of BM is that EQE curve graph is as shown in Figure 6 under 1:1 (w/w, 12mg/mL)；
The EQE test scope that the figure is shown is 300-800nm, there is maximum EQE value at 610nm, is 78.64%.
DFT(TDPP-TZ)2With PC71The J of single-electron device when the mixed proportion of BM is 1:1 (w/w, 12mg/mL)1/2- V is bent
Line is as shown in fig. 7, its hole mobility is up to 4.95 × 10-4cm2V-1s-1。
Embodiment 11
DFT(TDPP-TZS)2Photophysics and its small molecule photovoltaic device performance
DFT(TDPP-TZS)2Thermogravimetric curve figure it is as shown in Figure 8, decomposition temperature be 367 DEG C.
DFT(TDPP-TZS)2In CHCl3Ultra-violet absorption spectrum in solution is as shown in Figure 9.The wherein absorption of 377nm or so
Peak is the π-π * transition absorption peak of the small molecule material, and the absorption peak of 632nm or so is that donor monomer (DFT) arrives receptor unit
(DPP) electric charge transfer (ICT) transition absorption peak.
DFT(TDPP-TZS)2Ultra-violet absorption spectrum in solid film is as shown in Figure 10.Wherein the peak shape of absorption spectrum is big
Cause identical, but absorption peak has different degrees of red shift, this is because in solid film caused by pi-pi accumulation.Peak position calculates by
The band gap of the material is 1.57eV out.
DFT(TDPP-TZS)2Cyclic voltammetry curve in solid film is as shown in figure 11.It shows two groups of reversible oxygen
Change peak, the oxidation peak of donor monomer DFT and receptor unit DPP can be attributed to respectively.Thus obtain the material HOMO energy level be-
5.25eV。
DFT(TDPP-TZS)2With PC71The mixed proportion of BM is J-V curve graph such as Figure 12 under 1:1 (w/w, 12mg/mL)
It is shown.Under this condition, the short circuit current of device is 16.75mA/cm2, open-circuit voltage 0.795V, fill factor is
66.93%, photovoltaic efficiency 8.91%.
DFT(TDPP-TZS)2With PC71The mixed proportion of BM is EQE curve graph such as Figure 13 institute under 1:1 (w/w, 12mg/mL)
Show.The EQE test scope that the figure is shown is 300-800nm, has maximum EQE value at the place 661nm or so, is 78.89%.
DFT(TDPP-TZS)2With PC71The J of single-electron device when the mixed proportion of BM is 1:1 (w/w, 12mg/mL)1/2-V
Curve is as shown in figure 14, and hole mobility is up to 7.78 × 10-4cm2V-1s-1。
Despite the incorporation of preferred embodiment, the present invention is described, but the present invention is not limited to the above embodiments,
It should be understood that appended claims summarise the scope of the present invention.Under the guidance of present inventive concept, those skilled in the art
It should be recognized that certain change that various embodiments of the present invention scheme is carried out, it all will be by claims of the present invention
Spirit and scope covered.
Claims (10)
1. the D (A-Ar) of a kind of alkyl/sulfanyl nitrogen heteroaromatic rings end2Type conjugated compound, which is characterized in that D (A-Ar)2Type
The structural formula of conjugated compound is shown in formula I:
Wherein, A is to draw electronics bridge linkage group；D is center electron donating group；X=O, S, Se or Te；Y=O or S, R1It is independent
For C6~C8Alkyl.
2. alkyl according to claim 1/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2Type conjugated compound, feature
It is, the drawing electronics bridge linkage group A selects one of having structure:
R independently is C in said units6~C12Alkyl；
Center electron donating group D selects one of having structure:
R independently is C in said units6~C12Alkyl；
End alkyl/sulfanyl nitrogen heteroaromatic rings (Ar) group selects one of having structure:
R independently is C in said units6~C12Alkyl.
3. alkyl according to claim 1/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2Type conjugated compound, feature
It is, the D (A-Ar)2Type conjugated compound are as follows:
4. alkyl according to claim 3/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2The preparation side of type conjugated compound
Method, which is characterized in that the preparation method is as follows:
Side chain DPP-TZ-Br:2 is synthesized, 5- dibromo thiophene base pyrrolo-pyrrole-dione is under the action of tetra-triphenylphosphine palladium, with 2-
Stille coupling reaction occurs for octyl -5- thiazole tributyl tin, and synthesis obtains unilateral brominated DPP-TZ-Br crude product, through column
Chromatography obtains sterling；
Or, synthesis side chain DPP-TZS-Br:2,5- dibromo thiophene base pyrrolo-pyrrole-dione under the action of tetra-triphenylphosphine palladium,
Stille coupling reaction occurs with 2- sulphur octyl -5- thiazole tributyl tin, synthesis obtains unilateral brominated DPP-TZS-Br and slightly produces
Product obtain sterling through column chromatography for separation；
It synthesizes target molecule DFT (TDPP-TZ)2Or DFT (TDPP-TZS)2: side chain DPP-TZ-Br or DPP-TZS-Br and double fluorine
Stille coupling reaction occurs under tetra-triphenylphosphine palladium catalysis for bithiophene, and synthesis obtains D (A-Ar)2Type small molecule photovoltaic material
DFT(TDPP-TZ)2Or DFT (TDPP-TZS)2, crude product obtains sterling through column chromatography for separation.
5. described in any item alkyl/sulfanyl nitrogen heteroaromatic rings end D (A-Ar) according to claim 1~32Type is conjugated chemical combination
The application of object, which is characterized in that by the D (A-Ar)2Type conjugated compound and PC71BM is blended, and makes small molecule photovoltaic device
Part.
6. alkyl according to claim 5/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2The application of type conjugated compound,
It is characterized in that, D (A-Ar)2Type conjugated compound is applied to organic solar batteries, organic effect crystal as active layer
In pipe, organic electroluminescent LED or organic near infrared photodetector.
7. alkyl according to claim 5/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2The application of type conjugated compound,
It is characterized in that, the D (A-Ar)2Type conjugated compound and PC71It is 1:1 that mass ratio, which is blended, in BM.
8. alkyl according to claim 5/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2The application of type conjugated compound,
It is characterized in that, the anode modification layer of the small molecule photovoltaic device is poly- ethylenedioxythiophene (PEDOT) coating.
9. alkyl according to claim 6/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2The application of type conjugated compound,
It is characterized in that, the thickness of active layer is between 20 nanometers~1000 nanometers.
10. alkyl according to claim 6/sulfanyl nitrogen heteroaromatic rings sealing end D (A-Ar)2The application of type conjugated compound,
It is characterized in that, the active layer is realized by solution processing method.
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