CN115197219A - Non-benzene type perylene diimide conjugated condensed ring molecule and preparation method and application thereof - Google Patents
Non-benzene type perylene diimide conjugated condensed ring molecule and preparation method and application thereof Download PDFInfo
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- CN115197219A CN115197219A CN202110381085.2A CN202110381085A CN115197219A CN 115197219 A CN115197219 A CN 115197219A CN 202110381085 A CN202110381085 A CN 202110381085A CN 115197219 A CN115197219 A CN 115197219A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 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 title claims abstract description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title description 6
- 230000005669 field effect Effects 0.000 claims abstract description 24
- 239000004065 semiconductor Substances 0.000 claims abstract description 16
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 90
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 23
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 229910052740 iodine Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 239000003504 photosensitizing agent Substances 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 4
- -1 perylene diimide compound Chemical class 0.000 claims description 4
- 238000007363 ring formation reaction Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract 1
- 230000005012 migration Effects 0.000 abstract 1
- 238000007039 two-step reaction Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 6
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 238000004896 high resolution mass spectrometry Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003384 small molecules Chemical class 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229940125773 compound 10 Drugs 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 4
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- KRSBPXGBUCAYSC-UHFFFAOYSA-N azulene benzene Chemical group C1=CC=CC=C1.C1=CC=C2C=CC=CC=C12 KRSBPXGBUCAYSC-UHFFFAOYSA-N 0.000 description 3
- 125000003828 azulenyl group Chemical group 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- HPJFXFRNEJHDFR-UHFFFAOYSA-N 22291-04-9 Chemical compound C1=CC(C(N(CCN(C)C)C2=O)=O)=C3C2=CC=C2C(=O)N(CCN(C)C)C(=O)C1=C32 HPJFXFRNEJHDFR-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 150000001545 azulenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000003818 flash chromatography Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000010200 validation analysis Methods 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 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 1
- 230000004927 fusion Effects 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 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 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
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- 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
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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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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
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- Y02E10/549—Organic PV cells
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Abstract
The invention discloses perylene diimide conjugated condensed ring molecules containing azulene, a preparation method thereof and application thereof in the field effect transistor field. The structural formula is shown as formula I 1 ，I 2 ，I 3 ，I 4 ，I 5 ，I 6 ，I 7 And I 8 As shown. The perylene diimide condensed ring system containing azulene and having near infrared absorption is obtained through two-step reaction separation, both the perylene diimide condensed ring system show p-type semiconductor performance, and the hole migration of 7 and 10The shift rates respectively reach 10 ‑4 cm 2 V ‑1 s ‑1 And 4X 10 ‑3 cm 2 V ‑1 s ‑1 And has near infrared absorption characteristics.
Description
Technical Field
The invention belongs to the field of organic synthesis and photoelectric materials, and particularly relates to preparation of perylene diimide conjugated condensed ring molecules containing azulene, exploration of photophysical properties and application of the perylene diimide conjugated condensed ring molecules in the field effect transistor field.
Background
In the past decades, the research on polymer semiconductor materials has become relatively mature, and the mobility of many polymer semiconductor materials reaches the amorphous silicon level. However, the polymer cannot be accurately measured in composition, structure, stacking mode and the like, so that the application of the polymer in device research is limited. In contrast, organic small molecules are increasingly used for mechanism research in the carrier transport process due to their specific structures and compositions. For example, several small molecule backbones such as pyrrolopyrroledione (DPP), naphthalene Diimide (NDI), perylene Diimide (PDI) have been widely used and gradually developed into star molecules. Therefore, the development of a novel small molecular framework with a determined structure has important significance on the mechanism understanding and the material development of the organic semiconductor.
Non-benzene molecular azulenes fused by five-membered rings and seven-membered rings have received more and more attention in organic field effect transistors due to their unique chemical structures and electron distribution characteristics. The introduction of the azulene ring can change the characteristics of the conjugated skeleton, such as planarity, electron distribution, dipole, and the like to a great extent, thereby changing the photophysics and semiconductor performance of the semiconductor. Therefore, the azulene unit is combined with some rigid semiconductor frameworks, the photoelectric property of molecules is regulated and controlled through the expansion of the conjugation degree, and the research on the transmission process and mechanism of current carriers is very necessary. As an emerging field of research, the study of the fusion of azulenes into conjugated molecules has been reported to date in only a few cases. The perylene bisimide (PDI) system with the fused azulene ring to electron-withdrawing skeleton has never been reported.
Disclosure of Invention
One of the purposes of the invention is to develop a conjugated molecular material fused by perylene diimide and non-benzene azulene rings, develop a preparation method of the material, synthesize a series of derivatives with various structures, and research the application of the derivatives as materials of organic field effect transistors, chiral optics and the like.
The perylene diimide and azulene fused compound provided by the invention comprises eight groups, and the structural formula of the compound is shown as the formula I 1 ，I 2 ，I 3 ，I 4 ，I 5 ，I 6 ，I 7 And I 8 Shown in the specification:
the above formula I 1 ，I 2 ，I 3 ，I 4 ，I 5 ，I 6 ，I 7 And I 8 In, R 1 Can be independently H, C6-C18 straight chain alkyl (specifically can be (-C) 6 H 13 ) C6-C39 branched alkyl (specifically may be- (CH) 2 )CH(C 8 H 17 )(C 10 H 21 ) And a substituted or unsubstituted phenyl group;
wherein, the substituent in the substituted phenyl can be at least one of H, C1-C6 branched or branched alkyl, C1-C6 alkoxy, fluorine, chlorine, bromine and iodine, and can be 2, 6-diisopropyl;
the formula I 1 ，I 2 ，I 3 ，I 4 ，I 5 ，I 6 ，I 7 And I 8 In, R 2 Can be independently selected from H, C1-C18 straight chain or branched chain alkyl (specifically can be (-C (CH) 3 ) 3 ) F, cl, br, I and cyano.
The above formula I 1 ，I 2 ，I 3 ，I 4 ，I 5 ，I 6 ，I 7 And I 8 The compound shown can be specifically:
the above formula I 1 ，I 2 ，I 3 ，I 4 ，I 5 ，I 6 ，I 7 And I 8 The perylene diimide compound is prepared by a method comprising the following steps:
1) Represented by formula II 1 ，Ⅱ 2 ，Ⅱ 3 A compound of the formula II 4 ，Ⅱ 5 ，Ⅱ 6 And II 7 The compounds respectively generate coupling reaction under the catalysis of palladium tetratriphenylphosphine to obtain a compound shown in a formula III 1 -formula III 8 A compound shown as the formula (I);
above formula II 1 Formula II 2 And formula II 3 In, R 1 May independently be H, a straight chain alkyl group of C6-C18 (specifically may be (-C) 6 H 13 ) C6-C39 branched alkyl (specifically may be- (CH) 2 )CH(C 8 H 17 )(C 10 H 21 ) And a substituted or unsubstituted phenyl group;
wherein, the substituent in the substituted phenyl can be at least one selected from H, C1-C6 branched or branched alkyl, C1-C6 alkoxy, fluorine, chlorine, bromine and iodine, and can be 2, 6-diisopropyl;
above formula II 4 ，Ⅱ 5 ，Ⅱ 6 And II 7 In, R 2 Can be independently selected from H, C1-C18 straight chain or branched chain alkyl (specifically can be (-C (CH) 3 ) 3 ) Any one of F, cl, br, I and cyano;
formula III 1 -Ⅲ 8 In, R 1 Can be independently H, C6-C18 straight chain alkyl (specifically can be (-C) 6 H 13 ) C6-C39 branched alkyl (specifically may be- (CH) 2 )CH(C 8 H 17 )(C 10 H 21 ) And a substituted or unsubstituted phenyl group;
wherein, the substituent in the substituted phenyl can be at least one selected from H, C1-C6 branched or branched alkyl, C1-C6 alkoxy, fluorine, chlorine, bromine and iodine, and can be 2, 6-diisopropyl;
R 2 can be independently selected from H, C1-C18 straight chain or branched chain alkyl (specifically can be (-C (CH) 3 ) 3 ) Any one of F, cl, br, I and cyano;
2) Under the condition of illumination, the formula III 1 -formula III 8 The compound is subjected to cyclization reaction, separated and purified to obtain the compound shown in the formula I 1 ，I 2 ，I 3 ，I 4 ，I 5 ，I 6 ，I 7 And I 8 The compounds shown.
In step 1) of the above process, formula II 1 Formula II 4 Formula II 5 Formula II 6 And formula II 7 Are all synthesized by known literature methods (chem.Commun., 2015,51,12585, J.org.chem.2018,83, 1298-1303); formula II 2 And formula II 3 The compounds shown are mixtures directly available from the reagent company, in a ratio of approximately 3:1, separating by HPLC to obtain two pure compounds;
formula II 1 、Ⅱ 2 Or II 3 A compound of the formula II 4 、Ⅱ 5 、Ⅱ 6 Or II 7 The molar ratio of the compound and palladium triphenylphosphine is as follows: 1, 2.1-5.0; specifically, the ratio of 1
The temperature of the coupling reaction can be 90-120 ℃, and specifically can be 110 ℃; the time can be 6-48h, and specifically can be 12h;
the reaction is carried out in a nitrogen atmosphere;
the coupling reaction is carried out in an organic solvent, wherein the organic solvent can be toluene and tetrahydrofuran;
the step 1) further comprises the following separation and purification operations: and (3) carrying out spin drying on the solvent in the system after the coupling reaction, and carrying out column chromatography separation by using petroleum ether/dichloromethane (3 1 And formula III 2 Formula III 3 Formula III 4 And formula III 5 And formula III 6 And formula III 7 And formula III 8 Dissolving the compound in chloroform solvent, slowly adding methanol until solid is separated out, standing for a period of time, filtering out the solid, and finally washing with methanol to obtain the compound shown in the formula III 1 And formula III 2 Formula III 3 Formula III 4 And formula III 5 And formula III 6 And formula III 7 And formula III 8 A compound shown in the specification;
in step 2), the light source may be one of ultraviolet, visible light and blue light, specifically, may be a blue LED;
adding a photosensitizer in the step 2), wherein the photosensitizer can be I 2 (ii) a The added photosensitizer can be 0.2-20 equivalent;
the illumination time can be 48-100h, specifically 72h;
the reaction temperature can be 25-90 ℃, and particularly can be 85 ℃;
the cyclization reaction is carried out in a solvent, wherein the solvent can be toluene and dichloromethane, and can be toluene specifically;
the reaction is carried out under an air atmosphere;
the step 2) further comprises the operations of separation and purification: spin-drying the system after the cyclization reaction, removing the excess photosensitizer in the system by using petroleum ether as an eluent, and then using petroleum ether/dichloromethane (3 1 -I 8 Further recrystallizing the compound to obtain the compound I with higher purity 1 -I 8 A compound shown in the specification;
it is a further object of the present invention to provide compounds of formula I above 1 ，I 2 ，I 3 ，I 4 ，I 5 ，I 6 ，I 7 And I 8 The application of the compound as a p-type semiconductor material.
The application may be in particular of formula I 1 ，I 2 ，I 3 ，I 4 ，I 5 ，I 6 ，I 7 And I 8 The application of the compound in preparing a field effect device,
the field effect transistor device exhibits p-type charge transport properties.
The invention also provides a field effect device and a preparation method thereof.
The field effect device provided by the invention adopts the structure I 1 、I 2 、I 3 、I 4 、I 5 、I 6 、I 7 Or I 8 The compound shown is a p-type semiconductor material.
The field effect device is prepared by a method comprising the following steps:
the formula I is 1 、I 2 、I 3 、I 4 、I 5 、I 6 、I 7 Or I 8 The compound is evaporated on a substrate to prepare the field effect device;
in the preparation method, the thickness of the evaporated film can be 15nm, the evaporation rate can be 0.02-0.05 angstrom/s, and the substrate temperature is 20 ℃;
the preparation and the test of the field effect device are carried out in a nitrogen atmosphere;
the substrate is a common substrate known in the art, the electrode is a gold electrode, and the gold electrode is directly used after being modified by ultraviolet ozone treatment and Octadecyl Trichlorosilane (OTS) and cleaned.
It is also an object of the invention to provide small molecule materials with near infrared absorption.
The material may be in particular of the formula I 1 、I 2 、I 3 、I 4 、I 5 、I 6 、I 7 Or I 8 Materials made of the compounds shown;
the test method provided by the invention is that I 1 、I 2 、I 3 、I 4 、I 5 、I 6 、I 7 Or I 8 The compound is dissolved in chloroform solution with the concentration of 10 -5 mol/L；
The small molecule I 1 And I 3 The maximum absorption wavelengths of (a) are: 793nm and 807nm.
The invention has the following advantages:
the invention develops the condensed molecular skeleton of the non-benzene azulene ring and the perylene bisimide for the first time; provided formula I 1 -I 8 The compound has excellent hole transmission performance and dissolution performance, and is beneficial to researching the semiconductor performance of the compound; all of them show near infrared absorption characteristics and have larger molar extinction coefficient, so that the compound has potential application value in the aspect of photo-thermal.
Drawings
FIG. 1 shows formula I of the present invention 1 And I 3 A preparation method of the compound.
FIG. 2 shows formula I in example 1 of the present invention 1 Crystal structure of said compound.
FIG. 3 is a photograph of formula I prepared in example 1 of the present invention 1 And I 3 Ultraviolet-visible absorption spectrum of chloroform solution of the compound shown.
FIG. 4 is a graph of formula I prepared in example 1 of the present invention 1 And I 3 Cyclic voltammograms of the compounds shown.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The perylene diimide and azulene fused compound provided by the invention comprises eight groups, and the structural formula of the compound is shown as the formula I 1 ，I 2 ，I 3 ，I 4 ，I 5 ，I 6 ，I 7 And I 8 Shown in the figure:
the above formula I 1 ，I 2 ，I 3 ，I 4 ，I 5 ，I 6 ，I 7 And I 8 In, R 1 May independently be H, a straight chain alkyl group of C6-C18 (specifically may be (-C) 6 H 13 ) C6-C39 branched alkyl (specifically may be- (CH)) 2 )CH(C 8 H 17 )(C 10 H 21 ) And a substituted or unsubstituted phenyl group;
wherein, the substituent in the substituted phenyl can be at least one of H, C1-C6 branched or branched alkyl, C1-C6 alkoxy, fluorine, chlorine, bromine and iodine, and can be 2, 6-diisopropyl;
the formula I 1 ，I 2 ，I 3 ，I 4 ，I 5 ，I 6 ，I 7 And I 8 In, R 2 Can be independently selected from H, C1-C18 straight chain or branched chain alkyl (specifically can be (-C (CH) 3 ) 3 ) F, cl, br, I and cyano.
The invention also provides the formula I 1 ，I 2 ，I 3 ，I 4 ，I 5 ，I 6 ，I 7 And I 8 The compound is applied as a p-type semiconductor material.
The application may be in particular of formula I 1 ，I 2 ，I 3 ，I 4 ，I 5 ，I 6 ，I 7 And I 8 The use of the compounds shown in the preparation of field effect devices,
the field effect transistor device exhibits p-type charge transport properties.
The invention also provides a field effect device and a preparation method thereof.
The field effect device provided by the invention adopts the structure I 1 、I 2 、I 3 、I 4 、I 5 、I 6 、I 7 Or I 8 The compound shown is a p-type semiconductor material.
It is yet another object of the present invention to provide small molecule materials with near infrared absorption.
The material may be in particular represented by formula I 1 、I 2 、I 3 、I 4 、I 5 、I 6 、I 7 Or I 8 Materials made of the compounds shown.
The invention develops the condensed molecular skeleton of the non-benzene azulene ring and the perylene bisimide for the first time; provided formula I 1 -I 8 The compound has excellent hole transmission performance and dissolution performance, and is beneficial to researching the semiconductor performance of the compound; all of them show near infrared absorption characteristics and have larger molar extinction coefficient, so that the compound has potential application value in the aspect of photo-thermal.
Example 1, formula I 1 And I 3 Synthesis of the Compound (in the formula I, R 1 Is n-hexyl, R 2 Is tert-butyl; formula I 3 In, R 1 Is octyl dodecyl, R 2 As hydrogen atoms):
the chemical reaction flow chart is shown in figure 1, and the specific reaction step conditions are as follows:
formula I 1 The synthesis steps of the compound are as follows:
to a 50mL round-bottom flask containing magnetons were added Compound 1 (200mg, 0.28mmol), 4 (182mg, 0.7 mmol), sodium carbonate (222mg, 2.1 mmol) and Pd (PPh) 3 ) 4 (1695g, 0.014mmol). The mixture was degassed and purged with nitrogen three times. Toluene (15 mL), ethanol (5 mL) and water (5 mL) were then added to the flask. The mixture was heated at 110 ℃ for 12 hours. After cooling to room temperature, the reaction was quenched with water (10 mL) and the mixture was extracted with dichloromethane (30 mL. Times.3). The organic layer is coated with Na 2 SO 4 Dried and concentrated under reduced pressure. The crude product was then purified by flash column chromatography using petroleum ether (60-90 ℃) dichloromethane =2/1 as eluent to give 6 as a purple solid (161 mg, 71% yield).
The structure validation data is as follows:
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.63(d,J＝12Hz,2H),8.14(d,J＝12Hz,4H),7.98(s,2H),7.90(d,J＝8.0Hz,2H),7.35(s,4H),7.34-7.32(d,J＝8.0Hz,4H),3.58(t,J＝8.0Hz,4H),1.62(m,4H),1.47(s,18H),1.27(s,12H),0.85(t,J＝8.0Hz,6H)； 13 C NMR(100MHz,CDCl 3 ):δ168.6,167.6,161.1,149.6,140.1,138.1,136.6,135.7,134.5,133.4,129.7,128.9,127.3,124.6,124.2,121.9,121.5,115.6,38.2,37.5,31.4,30.9,28.1,26.1,22.0,13.5；
HR-MS: calculated value is C 64 H 62 N 2 O 4 (M + ): 922.4710, experimental test values: 922.4714;
from the above, the product structure is correct.
Compound 6 (15 mg. Times.2,0.037 mmol), iodine (20 mg. Times.2,0.15mmol) and toluene (10 mL. Times.2) were added to a quartz tube containing magnetons. The mixture was illuminated with a blue LED at 85 ℃ for 72 hours. After cooling to room temperature, filtration was carried out to obtain a crude residue. The crude product was then purified by column chromatography using dichloromethane/methanol =20/1 as eluent to give 7 (10 mg) as a brown solid in 23.5% yield.
The structure validation data is as follows:
1 H NMR(500MHz,CDCl 2 CDCl 2 )δ(ppm):9.74(d,J＝5.0Hz,2H),8.96(d,J＝5.0Hz,2H),8.74(d,J＝10.0Hz,2H),8.66(d,J＝10.0Hz,2H),8.08(s,2H),7.77(d,J＝10.0Hz,2H),7.58(d,J＝10.0Hz,2H),3.96(t,J＝10.0,4H),1.97-2.02(m,4H),1.66(s,18H),1.46-1.57(m,12H),1.01(t,J＝5.0,6H)； 13 C NMR(125MHz,CDCl 2 CDCl 2 ):δ168.3,167.8,159.7,139.4,138.1,137.8,135.7,134.9,124.6,124.3,123.5,123.2,123.0,122.5,122.2,121.0,121.0,120.4,119.3,119.2,116.1,110.3,37.3,36.9,30.4,30.3,27.5,25.3,21.1,12.6；
HR-MS: calculated value is C 64 H 58 N 2 O 4 (M - ): 918.4397, experimental test values: 918.4400;
from the above, the product structure is correct.
Formula I 3 Synthetic routes to the compounds shown:
to a 100mL round-bottomed flask containing magnetons were added compound 2 (300mg, 0.27mmol), 5 (206mg, 0.81mmol), sodium carbonate (214mg, 2mmol) and Pd (PPh) 3 ) 4 (31mg, 0.027mmol). The mixture was degassed and purged with nitrogen three times. Toluene (20 mL), ethanol (8 mL) and water (8 mL) were then added to the flask. The mixture was heated at 110 ℃ for 12 hours. After cooling to room temperature, the reaction was quenched with water (10 mL) and the mixture was extracted with dichloromethane (30 mL. Times.3). The organic layer was washed with Na 2 SO 4 Dried and concentrated under reduced pressure. The crude product was then purified by flash column chromatography using petroleum ether (60-90 ℃) dichloromethane =2/1 as eluent to give solids 8 (90 mg, 27.7% yield) and 9 (188 mg, 57.9% yield).
The structure confirmation data is as follows:
compound 8
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.72(s,2H),8.26(d,J＝12.0Hz,4H),8.99(d,J＝8.0Hz,2H),7.87(d,J＝8.0Hz,2H),7.61(t,J＝8.0Hz,2H),7.50(s,4H),7.58(d,J＝10.0Hz,2H),7.21(t,J＝8.0Hz,2H),4.12(d J＝8.0,4H),1.96-2.00(m,2H),1.12-1.41(m,64H),0.80-0.85(m,12H)； 13 C NMR(100MHz,CDCl 3 ):δ162.8,149.4,140.8,136.9,136.4,136.0,135.2,133.7,131.8,128.9,128.3,128.0,126.5,123.2,121.2,121.0,115.3,43.7,35.6,30.9,30.7,29.0,28.6,28.6,28.6,28.3,28.3,25.5,21.6,13.1；
HR-MS: calculated value is C 84 H 102 N 2 O 4 (M - ): 1202.7840, experimental test values: 1202.7848;
from the above, the product structure was correct.
Compound 9
1 H NMR(400MHz,CDCl 3 )δ(ppm):9.52(s,1H),9.00(s,1H),8.99(d,J＝8.0Hz,1H),8.67(s,1H),8.37(d,J＝12.0Hz,2H),8.31(d,J＝12.0Hz,1H),8.23(d,J＝8.0Hz,1H),8.09(d,J＝8.0Hz,1H),7.70(d,J＝8.0Hz,2H),7.66(d,J＝4.0Hz,1H),7.51(s,2H),7.26-7.43(m,4H),4.10(d,J＝8.0,2H),4.22(d,J＝8.0,2H),1.98(m,1H),2.08(m,1H),1.15-1.44(m,64H),0.76-0.84(m,12H)； 13 C NMR(100MHz,CDCl 3 ):δ164.1,163.7,163.7,163.6,152.1,141.9,141.4,140.9,138.0,137.7,137.3,132.8,130.4,127.1,126.0,125.5,124.2,123.9,123.4,122.0,121.9,121.0,120.7,120.5,116.1,45.1,44.7,37.0,36.9,31.9,31.9,31.9,30.2,30.2,29.8,29.7,29.7,29.7,29.7,29.4,29.3,26.7,26.6,22.7,22.7,22.6；
HR-MS: calculated value is C 84 H 100 N 2 O 4 (M - ): 1200.7683, experimental test values are: 1200.7679;
from the above, the product structure is correct.
Compound 8, compound 9 (70 mg. Times.2, 0.11mmol), iodine (80 mg. Times.2, 0.63mmol), toluene (15 mL. Times.2), and propylene oxide (1 mL. Times.2) were added to a quartz tube containing magnetons. The mixture was illuminated with a blue LED at 85 ℃ for 20 hours. After cooling to room temperature, the solvent was spin-dried. The crude product was then purified by column chromatography using petroleum ether/dichloromethane =1/1 as eluent to give 10 (91 mg) as a red-brown solid in 65% yield.
The structure confirmation data is as follows:
1 H NMR(400MHz,CDCl 3 )δ(ppm):10.10(s,2H),9.60(s,2H),9.57(d,J＝10.0Hz,2H),8.65(d,J＝10.0Hz,2H),8.25(s,2H),7.93(t,J＝10.0Hz,2H),7.78(t,J＝10.0Hz,2H),7.54(t,J＝10.0Hz,2H),4.24(d,J＝5.0Hz,4H),2.14-2.17(m,2H),1.13-1.30(m,64H),0.74-0.81(m,12H)；
HR-MS: calculated value is C 84 H 98 N 2 O 4 (M - ): 1198.7527, experimental test values: 1198.7522;
from the above, the product structure was correct.
Example 2 formula I 1 Crystal structure and packing of the compounds shown:
preparation of crystals: examples of the invention1 preparation of I 1 The compound (R2 is tert-butyl) is dissolved in a toluene solution, and is obtained by slowly diffusing methanol in the toluene solution through a diffusion method.
The crystal structure and the stacking of the compound are shown in figure 2, and the compound is saddle-shaped in the crystal, shows a larger twist angle and shows spiral chirality. The molecules show weak pi-pi interaction, and the distance of pi-pi is
Example 3, formula I 1 And I 3 Ultraviolet-visible absorption spectrum of the compound in chloroform solution:
the compound (I) obtained in example 1 of the present invention 1 And I 3 Compounds shown) are dissolved in a variety of organic solvents including chloroform, o-dichlorobenzene, 1, 2-tetrachloroethane, and other solvents such as: toluene, tetrahydrofuran, and the like. The compounds of the present invention have good solubility in chlorinated solvents. By reacting a compound of the formula I 1 And I 3 The absorption spectrum of the compound in chloroform is shown in FIG. 3. As can be seen from fig. 3, the longest absorption wavelengths of compounds 7 and 10 were 793nm and 807nm, respectively, and both showed good near infrared absorption characteristics.
Example 4 measurement of front-line orbital levels (HOMO and LUMO levels) using cyclic voltammetry:
the electrochemical workstation was used to test the formula I obtained in example 1 of the present invention 1 And I 3 The electrochemical properties of the compounds were tested using a three-electrode test system with a glassy carbon electrode as the working electrode, an Ag/AgCl electrode as the reference electrode, and a platinum wire electrode as the counter electrode. Cyclic voltammetry curves for 7 and 10 ultra dry methylene chloride solutions were measured using tetrabutylammonium hexafluorophosphate as supporting electrolyte (0.1 mol/L) and ferrocene as internal standard at a scan rate of 100mV/s, as shown in FIG. 4. As can be seen from FIG. 4, the HOMO and LUMO energy levels of Compound 7 are-4.83V and-3.58V, respectively, and Compound 10The HOMO and LUMO energy levels of-5.13V and-3.72V, respectively.
Example 5, preparation of field effect device:
according to the method of the literature (chem. Rev.2012,112, 2208-2267), a layer of silicon dioxide with a thickness of 300nm is plated on monocrystalline silicon, which is then plated with gold by means of photolithography, with a width of 1440 microns and a length of 50 microns, the surface is first treated with uv ozone and then modified with a monomolecular layer of octadecyltrichlorosilane.
The compound 7 prepared in example 1 of the present invention was vapor-deposited on the above-modified sheet. The substrate temperature during evaporation is 20 ℃, a field effect device of the compound is prepared, and the field effect property of the field effect device is tested;
the compound 10 prepared in the embodiment 1 of the invention is prepared into 5mg/mL chloroform solution, and is thrown onto the modified sheet by a spin coating method. The rotating speed is set to be 2500r/min, and the film throwing time is 50s. Annealing the film-spun sheet at 80 ℃,120 ℃,160 ℃ and 180 ℃ for 10min respectively to prepare a field effect device of the compound, and testing the field effect property of the field effect device;
under the nitrogen atmosphere, both compounds show p-type semiconductor properties, have larger on-off ratio, and the mobility of the compound 10 reaches 4 multiplied by 10 after annealing -3 cm 2 V -1 s -1 . The mobility of compound 7 was slightly lower than that of compound 10, up to 10 -4 cm 2 V -1 s -1 . It may be related to the fact that compound 7 showed a more pronounced distortion, poorer planarity than compound 10, and weaker intermolecular interactions. The results show that the synthesis of the non-benzene conjugated fused rings of different perylene diimides is realized by changing the structures of the perylene diimides and the position isomerism of azulene, and the regulation and control effect of the compound structure on the performance is illustrated by comparing the photophysical property and the electrical property of the perylene diimides.
Claims (9)
1. Perylene diimide and azulene fused compound, and structural formula thereof is shown in formula I 1 、I 2 、I 3 、I 4 、I 5 、I 6 、I 7 Or I 8 Shown in the figure:
formula I 1 ，I 2 ，I 3 ，I 4 ，I 5 ，I 6 ，I 7 And I 8 In, R 1 Independently is any one of H, C6-C18 linear alkyl, C6-C39 branched alkyl and substituted or unsubstituted phenyl;
wherein, the substituent in the substituted phenyl is selected from at least one of H, C1-C6 branched or branched alkyl, C1-C6 alkoxy, fluorine, chlorine, bromine and iodine;
R 2 independently selected from any one of H, C1-C18 straight chain or branched chain alkyl, F, cl, br, I and cyano.
2. The compound of claim 1, wherein: formula I 1 、I 2 、I 3 、I 4 、I 5 、I 6 、I 7 And I 8 The compounds shown are in turn:
3. a process for preparing a compound according to claim 1 or 2, which comprises: formula I 1 、I 2 、I 3 、I 4 、I 5 、I 6 、I 7 And I 8 The perylene diimide compound is prepared by a method comprising the following steps:
1) Represented by formula II 1 ，Ⅱ 2 ，Ⅱ 3 A compound of the formula II 4 ，Ⅱ 5 ，Ⅱ 6 And II 7 The compounds respectively generate coupling reaction under the catalysis of palladium tetratriphenylphosphine to obtain a compound shown in a formula III 1 -formula III 8 A compound shown in the specification;
formula II 1 And formula II 2 And formula II 3 In, R 1 Independently is any one of H, C6-C18 linear alkyl, C6-C39 branched alkyl and substituted or unsubstituted phenyl;
wherein, the substituent in the substituted phenyl is selected from at least one of H, C1-C6 branched or branched alkyl, C1-C6 alkoxy, fluorine, chlorine, bromine and iodine;
formula II 4 ，Ⅱ 5 ，Ⅱ 6 And II 7 In, R 2 Independently selected from any one of H, C1-C18 straight chain or branched chain alkyl, F, cl, br, I and cyano;
formula III 1 -Ⅲ 8 In, R 1 Independently is any one of H, C6-C18 linear alkyl, C6-C39 branched alkyl and substituted or unsubstituted phenyl;
wherein, the substituent in the substituted phenyl is selected from at least one of H, C1-C6 branched or branched alkyl, C1-C6 alkoxy, fluorine, chlorine, bromine and iodine;
R 2 independently selected from any one of H, C1-C18 straight chain or branched chain alkyl, F, cl, br, I and cyano;
2) Under the condition of illumination, the formula III 1 -formula III 8 The compound is subjected to cyclization reaction, separated and purified to obtain the compound shown in the formula I 1 ，I 2 ，I 3 ，I 4 ，I 5 ，I 6 ，I 7 And I 8 The compounds shown.
4. The method of claim 3, wherein: in step 1), formula II 1 、Ⅱ 2 Or II 3 A compound of the formula II 4 、Ⅱ 5 、Ⅱ 6 Or II 7 The molar ratio of the compound and palladium triphenylphosphine is as follows: 1, 2.1-5.0;
the temperature of the coupling reaction is 90-120 ℃; the time is 6-48h.
5. The method according to claim 3 or 4, characterized in that: in the step 2), the light source is one of ultraviolet light, visible light and blue light,
adding a photosensitizer I in the step 2) 2 (ii) a 0.2-20 equivalents of photosensitizer is added;
the illumination time is 48-100h;
the temperature of the reaction is 25-90 ℃.
6. Formula I according to claim 1 or 2 1 、I 2 、I 3 、I 4 、I 5 、I 6 、I 7 Or I 8 The application of the compound as a p-type semiconductor material.
7. Use according to claim 6, characterized in that: the application is of formula I 1 、I 2 、I 3 、I 4 、I 5 、I 6 、I 7 Or I 8 Use of the compounds shown for the preparation of a field effect transistor device exhibiting p-type charge transport properties.
8. A field effect device of formula I in claim 1 or 2 1 、I 2 、I 3 、I 4 、I 5 、I 6 、I 7 Or I 8 The compounds shown are p-type semiconductor materials.
9. Small with near infrared absorptionMolecular material, said material being represented by formula I in claim 1 or 2 1 、I 2 、I 3 、I 4 、I 5 、I 6 、I 7 Or I 8 Materials made of the compounds shown.
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| JPH05179237A (en) * | 1991-12-26 | 1993-07-20 | Konica Corp | Organic thin-film electroluminescent element |
| WO2009021663A1 (en) * | 2007-08-10 | 2009-02-19 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Doped semiconductor material and use thereof |
| CN104028308A (en) * | 2014-06-20 | 2014-09-10 | 中国科学院新疆理化技术研究所 | Nanometer photo-catalyst used in producing hydrogen by decomposing water under visible light response and application of nanometer photo-catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05179237A (en) * | 1991-12-26 | 1993-07-20 | Konica Corp | Organic thin-film electroluminescent element |
| WO2009021663A1 (en) * | 2007-08-10 | 2009-02-19 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Doped semiconductor material and use thereof |
| CN104028308A (en) * | 2014-06-20 | 2014-09-10 | 中国科学院新疆理化技术研究所 | Nanometer photo-catalyst used in producing hydrogen by decomposing water under visible light response and application of nanometer photo-catalyst |
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