CN111689994B - Organic conjugated molecular material with dibenzofuran Aza-BODIPY as basic skeleton and preparation method and application thereof - Google Patents
Organic conjugated molecular material with dibenzofuran Aza-BODIPY as basic skeleton and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 25
- 150000002367 halogens Chemical group 0.000 claims abstract description 25
- 239000012776 electronic material Substances 0.000 claims abstract description 6
- 238000012984 biological imaging Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 186
- 238000006243 chemical reaction Methods 0.000 claims description 97
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 96
- -1 n-dodecyloxy Chemical group 0.000 claims description 49
- 229910052763 palladium Inorganic materials 0.000 claims description 48
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 28
- 239000004327 boric acid Substances 0.000 claims description 25
- 239000007800 oxidant agent Substances 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 23
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 23
- 230000035484 reaction time Effects 0.000 claims description 20
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 20
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 19
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 16
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052794 bromium Inorganic materials 0.000 claims description 16
- 125000001246 bromo group Chemical group Br* 0.000 claims description 16
- 239000011630 iodine Chemical group 0.000 claims description 16
- 229910052740 iodine Chemical group 0.000 claims description 16
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 8
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 7
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 7
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 7
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 7
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 238000002329 infrared spectrum Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- 238000010521 absorption reaction Methods 0.000 description 43
- 238000005481 NMR spectroscopy Methods 0.000 description 42
- 238000006862 quantum yield reaction Methods 0.000 description 39
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- 150000002430 hydrocarbons Chemical group 0.000 description 28
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- 238000000862 absorption spectrum Methods 0.000 description 16
- 238000000295 emission spectrum Methods 0.000 description 16
- 238000002156 mixing Methods 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- MNJYZNVROSZZQC-UHFFFAOYSA-N (4-tert-butylphenyl)boronic acid Chemical compound CC(C)(C)C1=CC=C(B(O)O)C=C1 MNJYZNVROSZZQC-UHFFFAOYSA-N 0.000 description 5
- 125000006657 (C1-C10) hydrocarbyl group Chemical group 0.000 description 5
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- HXITXNWTGFUOAU-UHFFFAOYSA-N dihydroxy-phenylborane Natural products OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- WRKAFBNCCVUNQR-UHFFFAOYSA-N bromo(fluoro)boron Chemical compound F[B]Br WRKAFBNCCVUNQR-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 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
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 2
- 229960004657 indocyanine green Drugs 0.000 description 2
- MOFVSTNWEDAEEK-UHFFFAOYSA-M indocyanine green Chemical compound [Na+].[O-]S(=O)(=O)CCCCN1C2=CC=C3C=CC=CC3=C2C(C)(C)C1=CC=CC=CC=CC1=[N+](CCCCS([O-])(=O)=O)C2=CC=C(C=CC=C3)C3=C2C1(C)C MOFVSTNWEDAEEK-UHFFFAOYSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- RULQUTYJXDLRFL-UHFFFAOYSA-N (3,4,5-trimethoxyphenyl)boronic acid Chemical compound COC1=CC(B(O)O)=CC(OC)=C1OC RULQUTYJXDLRFL-UHFFFAOYSA-N 0.000 description 1
- XUIURRYWQBBCCK-UHFFFAOYSA-N (3,5-dimethoxyphenyl)boronic acid Chemical compound COC1=CC(OC)=CC(B(O)O)=C1 XUIURRYWQBBCCK-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- 238000004252 FT/ICR mass spectrometry Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N benzofuran Natural products C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
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- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
- C09K2211/107—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms with other heteroatoms
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- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
- C09K2211/1085—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms with other heteroatoms
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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
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses an organic conjugated molecular material taking dibenzofuran Aza-BODIPY as a basic framework, a preparation method and application thereof, wherein the structure of the organic conjugated molecular material is shown as a formula I, a formula II or a formula III, R1, R2, R3 and R4 in the formula are respectively and independently selected from one of hydrocarbon groups of H, C-C14 and hydrocarbon oxygen groups of C1-C14, and n1, n2, n3 and n4 are respectively and independently positive integers of 1-5; r5 is one of H and C1-C6 alkyl, and m is a positive integer from 1 to 4; r6 and R7 are each independently one of H and C1-C10 hydrocarbon groups, X is halogen, the organic conjugated molecular material has novel structure, excellent near infrared spectrum selectivity and high stability, can be applied to the fields of biological imaging, organic electronic materials and the like, and simultaneously has the advantages of mild condition and simple operation,
Description
Technical Field
The invention relates to an organic conjugated molecular material, in particular to an organic conjugated molecular material taking dibenzofuran Aza-BODIPY as a basic framework, and a preparation method and application thereof.
Background
Near infrared optical materials have important applications in the fields of organic electronic materials (e.g., light emitting diodes and organic field effect transistors) and the like; for example, the development of near infrared fluorescent dyes with high fluorescence quantum yields is critical to fluorescence imaging techniques; in addition, the long-wave dye is widely applied to cell imaging due to the advantages of high penetration, small damage, high sensitivity and the like, can prolong the absorption and emission wavelength of the dye, and has higher single-line oxygen efficiency.
However, the most commonly used near infrared fluorescent probes at present have the defects of poor stability, unstable fluorescent performance, high synthesis difficulty and the like, and are greatly restricted in application.
Disclosure of Invention
The invention aims to provide an organic conjugated molecular material taking dibenzofuran Aza-BODIPY as a basic framework, and a preparation method and application thereof.
In order to achieve the aim, the invention provides an organic conjugated molecular material taking dibenzofuran Aza-BODIPY as a basic framework, the structure of the organic conjugated molecular material is shown as a formula I, a formula II or a formula III,
Wherein R1, R2, R3 and R4 in the formula are each independently selected from one of a hydrocarbon group of H, C-C14 and a hydrocarbon group of C1-C14, and n1, n2, n3 and n4 are each independently positive integers of 1-5; r5 is one of H and C1-C6 alkyl, and m is a positive integer from 1 to 4; r6 and R7 are each independently one of H and C1-C10 hydrocarbyl, X is halogen.
The invention also provides a preparation method of the organic conjugated molecular material with the structure shown in the formula I, which comprises the following steps:
1) Under alkaline conditions, carrying out a first contact reaction on a compound with a structure shown in a formula 3, a fluorenyl boric acid compound and a palladium catalyst in a solvent to obtain a compound with a structure shown in a formula 9;
2) Carrying out a first oxidation reaction on a compound with a structure shown in a formula 9 and an oxidant in a solvent to prepare an organic conjugated molecular material with a structure shown in a formula I,
wherein R1, R2, R3 and R4 in the formula are each independently selected from one of a hydrocarbon group of H, C-C14 and a hydrocarbon group of C1-C14, n1, n2, n3 and n4 are each independently positive integers of 1-5, and X is halogen; the structure of the fluorenyl boric acid compound is shown as a formula 13-1 or a formula 13-2.
The invention also provides a preparation method of the organic conjugated molecular material with the structure shown in the formula II, which comprises the following steps:
1) Under alkaline conditions, carrying out a second contact reaction on a compound with a structure shown in a formula 5, a fluorenyl boric acid compound and a palladium catalyst in a solvent to obtain a compound with a structure shown in a formula 10;
2) Carrying out a second oxidation reaction on a compound with a structure shown in a formula 10 and an oxidant in a solvent to prepare an organic conjugated molecular material with a structure shown in a formula II;
wherein R1, R2, R3 and R4 in the formula are each independently selected from one of a hydrocarbon group of H, C-C14 and a hydrocarbon group of C1-C14, and n1, n2, n3 and n4 are each independently positive integers of 1-5; r5 is a hydrocarbon group of H, C1-C6, and m is a positive integer of 1-4; r6 and R7 are each independently one of H and C1-C10 hydrocarbyl, X is halogen; the structure of the fluorenyl boric acid compound is shown as a formula 13-1 or a formula 13-2.
The invention further provides a preparation method of the organic conjugated molecular material with the structure shown in the formula III, which comprises the following steps:
1) Under alkaline conditions, carrying out a third contact reaction on a compound with a structure shown in a formula 2, a fluorenyl boric acid compound and a palladium catalyst in a solvent to obtain a compound with a structure shown in a formula 11;
2) Carrying out a fourth contact reaction on a compound with a structure shown in a formula 11 and halogen source in a solvent to prepare an organic conjugated molecular material with a structure shown in a formula 12;
3) Carrying out a third oxidation reaction on a compound with a structure shown in a formula 12 and an oxidant in a solvent to prepare an organic conjugated molecular material with a structure shown in a formula II;
wherein R1, R2, R3 and R4 in the formula are each independently selected from one of a hydrocarbon group of H, C-C14 and a hydrocarbon group of C1-C14, and n1, n2, n3 and n4 are each independently positive integers of 1-5; r5 is a hydrocarbon group of H, C1-C6, and m is a positive integer of 1-4; r6 and R7 are each independently one of H and C1-C10 hydrocarbyl, X is halogen; the structure of the fluorenyl boric acid compound is shown as a formula 13-1 or a formula 13-2.
The invention further provides application of the organic conjugated molecular material taking the dibenzofuran Aza-BODIPY as a basic framework in biological imaging and organic electronic materials.
The inventors found that factors responsible for the decrease in fluorescence of dyes included the following: 1) The energy gap is narrowed, so that the non-radiative transition of the excited electrons between energy levels is facilitated; 2) Long wave compounds are usually accompanied by larger framework structures, and the framework vibration and the transformation of the excited state configuration can cause great energy loss; 3) The larger molecular structure increases the acting force among molecules, so that the dye is more easily gathered and the fluorescence is quenched; 4) The energy gap is narrowed such that interactions between the multiple state energy levels of the excited states cause the excited states to increase in non-radiative decay.
According to the technical scheme, the compound shown in the formula I) (II) (III) has a larger conjugated system and larger molecular rigidity, so that the compound has longer near infrared absorption wavelength and longer fluorescence emission wavelength and keeps higher fluorescence quantum yield, and can be applied to the fields of biological imaging, organic electronic materials and the like.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
FIG. 1 is a graph showing the absorption/emission spectrum of II-1 in test example 1;
FIG. 2 is a graph showing the absorption/emission spectrum of II-2 in test example 2;
FIG. 3 is a graph showing the absorption/emission spectrum of III-1 in test example 3;
FIG. 4 is a graph showing the absorption/emission spectrum of III-2 in test example 4;
FIG. 5 is a degradation profile of DPBF by III-1 and III-2 in test example 5.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides an organic conjugated molecular material with dibenzofuran Aza-BODIPY as basic skeleton, the structure of the organic conjugated molecular material is shown in formula I, formula II or formula III,
wherein R1, R2, R3 and R4 in the formula are each independently selected from one of a hydrocarbon group of H, C-C14 and a hydrocarbon group of C1-C14, and n1, n2, n3 and n4 are each independently positive integers of 1-5; r5 is one of H and C1-C6 alkyl, and m is a positive integer from 1 to 4; r6 and R7 are each independently one of H and C1-C10 hydrocarbyl, X is halogen.
In the above organic conjugated molecular material, the kind and number of each substituent may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the material, preferably, each of R1, R2, R3, R4 is independently selected from one of an alkyl group of H, C to C14 and an alkoxy group of C1 to C14, R5 is one of a hydrocarbon group of C1 to C6, each of R6 and R7 is independently one of H and an alkyl group of C1 to C10, and X is bromine or iodine; more preferably, each of R1, R2, R3, R4 is independently selected from one of H and C1-C12 alkoxy, R5 is one of C4-C6 hydrocarbyl, each of R6 and R7 is independently one of C8-C10 alkyl, and X is bromine or iodine; further preferably, each of R1, R2, R3, R4 is independently selected from methoxy or n-dodecyloxy, R5 is tert-butyl, R6 and R7 are each methyl or n-octyl, X is bromine or iodine, m, n1, n2, n3 and n4 are each 1 and represent a mono-substitution, and when m, n1, n2, n3 and n4 are greater than 1 are each a multi-substitution.
Still more preferably, the structure of the organic conjugated molecular material is shown as formula I-1, formula I-2, formula II-1, formula II-2, formula III-1 or formula III-2,
wherein C in the formula 8 H 17 Is n-octyl, C 12 H 25 O is n-dodecyloxy. C hereinafter 8 H 17 Are all n-octyl, C 12 H 25 O is n-dodecyloxy.
The invention also provides a preparation method of the organic conjugated molecular material with the structure shown in the formula I, which comprises the following steps:
1) Under alkaline conditions, carrying out a first contact reaction on a compound with a structure shown in a formula 3, a fluorenyl boric acid compound and a palladium catalyst in a solvent to obtain a compound with a structure shown in a formula 9;
2) Carrying out a first oxidation reaction on a compound with a structure shown in a formula 9 and an oxidant in a solvent to prepare an organic conjugated molecular material with a structure shown in a formula I,
wherein R1, R2, R3 and R4 in the formula are each independently selected from one of a hydrocarbon group of H, C-C14 and a hydrocarbon group of C1-C14, n1, n2, n3 and n4 are each independently positive integers of 1-5, and X is halogen; the structure of the fluorenyl boric acid compound is shown as a formula 13-1 or a formula 13-2.
In the above preparation method of the material having the structure shown in formula I, the kind and number of each substituent may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, preferably, each of R1, R2, R3, R4 is independently selected from one of an alkyl group of H, C1 to C14 and an alkoxy group of C1 to C14, and X is bromine or iodine; more preferably, R1, R2, R3 and R4 are each independently selected from H and one of C1-C12 alkoxy, and X is bromine or iodine; further preferably, each of R1, R2, R3, R4 is independently selected from methoxy or n-dodecyloxy, X is bromine or iodine, and n1, n2, n3, and n4 are all 1.
In the above preparation method of the material having the structure shown in formula I, the amount of the raw materials may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, preferably, in step 1), the compound having the structure shown in formula 3, the fluorenylboronic acid compound, and the palladium catalyst are used in a molar ratio of 1:2-4:0.05-0.1.
In the above-described method for producing a material having a structure represented by formula I, the conditions for the first contact reaction may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the produced material, it is preferable that the first contact reaction satisfies at least the following conditions: the reaction temperature is 90-120 ℃ and the reaction time is 24-36h.
In the above preparation method of the material having the structure shown in formula I, the pH of the reaction system may be selected within a wide range, but in order to further improve the yield of the product, preferably, in step 1), the pH of the reaction system is controlled by carbonate, and the molar ratio of the compound having the structure shown in formula 3 to carbonate is 1:2-6; further preferably, the carbonate is selected from at least one of sodium carbonate, potassium carbonate and cesium carbonate.
In the above preparation method of the material having the structure shown in formula I, the amount and kind of the oxidizing agent may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, preferably, in step 2), the amount of the compound having the structure shown in formula 9 and the oxidizing agent are used in a molar ratio of 1:4-15; more preferably, in step 2), the oxidizing agent is selected from at least one of anhydrous ferric trichloride, molybdenum pentachloride, and dichlorodicyanobenzoquinone;
in the above-described method for producing a material having a structure represented by formula I, the conditions for the first oxidation reaction may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the produced material, it is preferable that in step 2), the first oxidation reaction satisfies at least the following conditions: the reaction temperature is 0-45 ℃ and the reaction time is 10-30min.
In the above preparation method of the material having the structure shown in formula I, the kind of the palladium catalyst may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, it is preferable that the palladium catalyst is selected from at least one of tetraphenylphosphine palladium, palladium acetate, palladium chloride, bis (triphenylphosphine) palladium dichloride and tris (dibenzylideneacetone) dipalladium.
In the above preparation method of the material having the structure shown in formula I, the kind of the fluorenyl boric acid compound may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, it is preferable that the fluorenyl boric acid compound is 9, 9-dioctylfluorene-2, 7-bis boric acid or 9, 9-dioctylfluorene-2, 7-bis (pinacol borate).
In the above preparation method of the material having the structure shown in formula I, the kind of the compound having the structure shown in formula 3 may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, it is preferable that the structure of the compound having the structure shown in formula 3 is shown in formula 3-1 or formula 3-2,
the invention also provides a preparation method of the organic conjugated molecular material with the structure shown in the formula II, which comprises the following steps:
1) Under alkaline conditions, carrying out a second contact reaction on a compound with a structure shown in a formula 5, a fluorenyl boric acid compound and a palladium catalyst in a solvent to obtain a compound with a structure shown in a formula 10;
2) Carrying out a second oxidation reaction on a compound with a structure shown in a formula 10 and an oxidant in a solvent to prepare an organic conjugated molecular material with a structure shown in a formula II;
Wherein R1, R2, R3 and R4 in the formula are each independently selected from one of a hydrocarbon group of H, C-C14 and a hydrocarbon group of C1-C14, and n1, n2, n3 and n4 are each independently positive integers of 1-5; r5 is a hydrocarbon group of H, C1-C6, and m is a positive integer of 1-4; r6 and R7 are each independently one of H and C1-C10 hydrocarbyl, X is halogen; the structure of the fluorenyl boric acid compound is shown as a formula 13-1 or a formula 13-2.
In the above preparation method of the material having the structure shown in formula II, the kind and number of each substituent may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, preferably, each of R1, R2, R3, R4 is independently selected from one of an alkyl group of H, C1 to C14 and an alkoxy group of C1 to C14, R5 is a hydrocarbon group of C1 to C6, each of R6 and R7 is independently one of H and an alkyl group of C1 to C10, and X is bromine or iodine; more preferably, R1, R2, R3, R4 are each independently selected from one of H and C1-C12 alkoxy, R5 is C4-C6 hydrocarbyl, R6 and R7 are each independently one of C8-C10 alkyl, X is bromine or iodine; further preferably, each of R1, R2, R3, R4 is independently selected from methoxy or n-dodecyloxy, R5 is tert-butyl, R6 and R6 are each methyl or n-octyl, X is bromine or iodine, preferably, m, n1, n2, n3 and n4 are each 1, and n1 is a mono-substitution, and when m, n1, n2, n3 and n4 are greater than 1 is a multi-substitution.
In the above preparation method of the material having the structure shown in formula II, the amount of the raw materials may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, preferably, in step 1), the compound having the structure shown in formula 5, the fluorenylboronic acid compound, and the palladium catalyst are used in a molar ratio of 1:0.4-0.6:0.05-0.1.
In the above-described method for producing a material having a structure represented by formula II, the conditions for the second contact reaction may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the produced material, it is preferable that the second contact reaction satisfies at least the following conditions: the reaction temperature is 90-120 ℃ and the reaction time is 24-36h.
In the above preparation method of the material having the structure shown in formula II, the conditions of the second contact reaction may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, preferably, in step 1), the pH of the reaction system is controlled by carbonate, and the molar ratio of the compound having the structure shown in formula 5 to carbonate is 1:2-6; further preferably, the carbonate is selected from at least one of sodium carbonate, potassium carbonate and cesium carbonate;
In the above preparation method of the material having the structure shown in formula II, the amount and kind of the oxidizing agent may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, preferably, in step 2), the amount of the compound having the structure shown in formula 10 and the oxidizing agent are used in a molar ratio of 1:4-15; preferably, in step 2), the oxidizing agent is selected from at least one of anhydrous ferric trichloride, molybdenum pentachloride, and dichlorodicyanobenzoquinone.
In the above-described method for producing a material having a structure represented by formula II, the conditions for the second oxidation reaction may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the produced material, it is preferable that in step 2), the second oxidation reaction satisfies at least the following conditions: the reaction temperature is 0-45 ℃ and the reaction time is 10-30min.
In the above preparation method of the material having the structure shown in formula II, the kind of the palladium catalyst may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, it is preferable that the palladium catalyst is selected from at least one of tetraphenylphosphine palladium, palladium acetate, palladium chloride, bis (triphenylphosphine) palladium dichloride and tris (dibenzylideneacetone) dipalladium.
In the above preparation method of the material having the structure shown in formula II, the kind of the fluorenyl boric acid compound may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, it is preferable that the fluorenyl boric acid compound is 9, 9-dioctylfluorene-2, 7-bis boric acid or 9, 9-dioctylfluorene-2, 7-bis (pinacol borate);
in the above-described preparation method of the material having the structure shown in formula II, the kind of the compound having the structure shown in formula 5 may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, it is preferable that the structure of the compound having the structure shown in formula 5 is shown in formula 5-1 or formula 5-2,
the invention further provides a preparation method of the organic conjugated molecular material with the structure shown in the formula III, which comprises the following steps:
1) Under alkaline conditions, carrying out a third contact reaction on a compound with a structure shown in a formula 2, a fluorenyl boric acid compound and a palladium catalyst in a solvent to obtain a compound with a structure shown in a formula 11;
2) Carrying out a fourth contact reaction on a compound with a structure shown in a formula 11 and halogen source in a solvent to prepare an organic conjugated molecular material with a structure shown in a formula 12;
3) Carrying out a third oxidation reaction on a compound with a structure shown in a formula 12 and an oxidant in a solvent to prepare an organic conjugated molecular material with a structure shown in a formula II;
wherein R1, R2, R3 and R4 in the formula are each independently selected from one of a hydrocarbon group of H, C-C14 and a hydrocarbon group of C1-C14, and n1, n2, n3 and n4 are each independently positive integers of 1-5; r5 is a hydrocarbon group of H, C1-C6, and m is a positive integer of 1-4; r6 and R7 are each independently H or one of C1-C10 hydrocarbon groups, X is halogen, and the structure of the fluorenyl boric acid compound is shown as formula 13-1 or formula 13-2.
In the above preparation method of the material having the structure shown in formula III, the kind and number of each substituent may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, preferably, each of R1, R2, R3, R4 is independently selected from one of an alkyl group of H, C1 to C14 and an alkoxy group of C1 to C14, R5 is a hydrocarbon group of C1 to C6, each of R6 and R7 is independently one of H and an alkyl group of C1 to C10, and X is bromine or iodine; more preferably, R1, R2, R3, R4 are each independently selected from one of H and C1-C12 alkoxy, R5 is C4-C6 hydrocarbyl, R6 and R7 are each independently one of C8-C10 alkyl, X is bromine or iodine; further preferably, each of R1, R2, R3, R4 is independently selected from methoxy or n-dodecyloxy, R5 is tert-butyl, R6 and R6 are each methyl or n-octyl, X is bromine or iodine, preferably, m, n1, n2, n3 and n4 are each 1, and n1 is a mono-substitution, and when m, n1, n2, n3 and n4 are greater than 1 is a multi-substitution.
In the above preparation method of the material having the structure shown in formula III, the amount of the raw materials may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, preferably, in step 1), the compound having the structure shown in formula 2, the fluorenyl boric acid compound, and the palladium catalyst are used in a molar ratio of 1:0.4-0.6:0.05-0.1.
In the above-described method for producing a material having a structure represented by formula III, the conditions for the third contact reaction may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the produced material, it is preferable that, in step 1), the third contact reaction satisfies at least the following conditions: the reaction temperature is 90-120 ℃ and the reaction time is 24-36h.
In the above-described preparation method of the material having the structure shown in formula III, the pH of the reaction system may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, it is preferable that in step 1); more preferably, in step 1), the pH of the reaction system is controlled by carbonate, and the molar ratio of the compound having the structure shown in formula 2 to carbonate is 1:2-6; further preferably, the carbonate is selected from at least one of sodium carbonate, potassium carbonate and cesium carbonate.
In the above preparation method of the material having the structure shown in formula III, the amount and kind of the halogen source may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, preferably, in step 2), the molar ratio of the compound having the structure shown in formula 11 to the halogen source is 1:1.8-2.4; preferably, the halogen source is selected from at least one of liquid bromine, N-bromosuccinimide and elemental iodine.
In the above-described method for producing a material having a structure represented by formula III, the conditions for the fourth contact reaction may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the produced material, it is preferable that, in step 3), the fourth contact reaction satisfies at least the following conditions: the reaction temperature is 0-45 ℃ and the reaction time is 1-6h.
In the above preparation method of the material having the structure shown in formula III, the amount and kind of the oxidizing agent may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, preferably, in step 3), the amount of the compound having the structure shown in formula 12 and the oxidizing agent are used in a molar ratio of 1:4-15; preferably, in step 3), the oxidizing agent is selected from at least one of anhydrous ferric trichloride, molybdenum pentachloride, and dichlorodicyanobenzoquinone.
In the above-described method for producing a material having a structure represented by formula III, the conditions for the third oxidation reaction may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the produced material, it is preferable that in step 3), the third oxidation reaction satisfies at least the following conditions: the reaction temperature is 0-45 ℃ and the reaction time is 10-30min.
In the above-described preparation method of the material having the structure shown in formula III, the kind of the palladium catalyst may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, it is preferable that the palladium catalyst is at least one selected from the group consisting of tetraphenylphosphine palladium, palladium acetate, palladium chloride, bis (triphenylphosphine) palladium dichloride and tris (dibenzylideneacetone) dipalladium.
In the above preparation method of the material having the structure shown in formula III, the kind of the fluorenyl boric acid compound may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, it is preferable that the fluorenyl boric acid compound is 9, 9-dioctylfluorene-2, 7-bis boric acid or 9, 9-dioctylfluorene-2, 7-bis (pinacol borate);
In the above preparation method of the material having the structure shown in formula III, the kind of the structure of the compound having the structure shown in formula 2 may be selected within a wide range, preferably, the structure of the compound having the structure shown in formula 2 is shown in formula 2-1 or formula 2-2,
in the above-mentioned preparation methods of materials having structures represented by formulas I, II, and III, the raw materials used in the preparation methods of the materials having structures represented by formula 2, 3, and 5 may be commercially available products, or may be self-synthesized, and in order to improve the purity and reduce the cost, the present invention also discloses a preparation method of the compounds having structures represented by formula 2, 3, and 5, specifically as follows:
1) Carrying out a fifth contact reaction on a compound shown in a formula 1 and halogen source in a solvent to obtain a compound shown in a formula 2;
2) Carrying out a sixth contact reaction on a compound shown in a formula 1 and halogen source in a solvent to obtain a compound shown in a formula 3;
3) Under alkaline conditions, carrying out seventh contact reaction on a compound shown in a formula 2, a phenylboronic acid compound shown in a formula 14 and a palladium catalyst in a solvent to obtain a compound shown in a formula 4;
4) Carrying out eighth contact reaction on a compound shown as a formula 4 and halogen source in a solvent to obtain a compound shown as a formula 5;
wherein R1, R2, R3 and R4 in the formula are each independently selected from one of a hydrocarbon group of H, C-C14 and a hydrocarbon group of C1-C14, and n1, n2, n3 and n4 are each independently positive integers of 1-5; r5 is a hydrocarbon group of H, C1-C6, and m is a positive integer of 1-4; preferably, each of R1, R2, R3 and R4 is independently selected from one of H, C-C14 alkyl and C1-C14 alkoxy, and R5 is C1-C6 alkyl; more preferably, R1, R2, R3 and R4 are each independently selected from H and one of C1-C12 alkoxy, and R5 is a C4-C6 hydrocarbon group; preferably, m, n1, n2, n3 and n4 are all 1.
Further preferably, the structure of the compound represented by formula 1 is represented by formula 1-1 or 1-2,
in the fifth contact reaction, the amount of each raw material may be selected within a wide range, but in order to improve the yield, it is preferable that the molar ratio of the compound represented by formula 1 to the halogen source is 1:0.9-1.2.
In the sixth contact reaction, the amount of each raw material may be selected within a wide range, but in order to improve the yield, it is preferable that the molar ratio of the compound represented by formula 1 to the halogen source is 1:1.8-2.4.
In the seventh contact reaction, the amount of each raw material may be selected within a wide range, but in order to improve the yield, it is preferable that the molar ratio of the compound represented by formula 2 to the amount of the phenylboronic acid compound and the palladium catalyst is 1:1-4:0.05-0.1.
In the eighth contact reaction, the amount of each raw material may be selected within a wide range, but in order to improve the yield, it is preferable that the molar ratio of the compound represented by formula 4 to the halogen source is 1:0.9-1.2.
In the seventh contact reaction, the reaction temperature may be selected within a wide range, but in order to improve the yield, it is preferable that the reaction temperature of the third contact reaction is 90 to 120 ℃.
In the fifth, sixth and seventh contact reactions, the reaction temperature may be selected within a wide range, but in order to improve the yield, it is preferable that the reaction temperatures of the first, second and fourth contact reactions are each independently 0 to 45 ℃.
In addition, in the fifth contact reaction, the sixth contact reaction and the eighth contact reaction, the contact reaction time of each step may be selected within a wide range, but in order to make the reaction sufficient and to improve the yield, it is preferable that the fifth contact reaction time be 0.5 to 1h, the sixth contact reaction time be 0.5 to 2h, the seventh contact reaction time be 12 to 36h, and the eighth contact reaction time be 0.5 to 1h.
In the seventh contact reaction described above, the pH of the reaction system may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the produced material, preferably, in step 1), the pH of the reaction system is controlled by carbonate, and the molar ratio of the compound having the structure shown in formula 2 to carbonate is 1:2-6; further preferably, the carbonate is selected from at least one of sodium carbonate, potassium carbonate and cesium carbonate.
In the fifth contact reaction, the sixth contact reaction, and the eighth contact reaction, the kind of the halogen source may be selected from a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the produced material, it is preferable that the halogen source is selected from at least one of liquid bromine, N-bromosuccinimide, and elemental iodine.
In the above-described method for producing a material having a structure represented by formula III, the conditions for the eighth contact reaction may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the produced material, it is preferable that, in step 3), the eighth contact reaction satisfies at least the following conditions: the reaction temperature is 0-45 ℃ and the reaction time is 1-6h.
In the seventh contact reaction described above, the kind of the palladium catalyst may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the material produced, it is preferable that the palladium catalyst is selected from at least one of tetrakis triphenylphosphine palladium, palladium acetate, palladium chloride, bis (triphenylphosphine) palladium dichloride, and tris (dibenzylideneacetone) dipalladium.
In the seventh contact reaction described above, the kind of the phenylboronic acid compound may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the material produced, it is preferable that the phenylboronic acid compound is selected from at least one of 4-t-butylphenylboronic acid, 3, 5-dimethoxyphenylboronic acid and 3,4, 5-trimethoxyphenylboronic acid.
In each of the production methods of the present invention, the kind of the solvent may be selected from a wide range, and may be a halogenated hydrocarbon solvent such as one or more of methylene chloride, chloroform, trichloroethylene and 1, 2-dichloroethane; but also aromatic hydrocarbon solvents such as one or more of toluene, xylene, chlorobenzene and o-dichlorobenzene. The amount of the solvent is not particularly limited as long as the reaction raw material can be sufficiently dispersed.
The invention further provides application of the organic conjugated molecular material taking the dibenzofuran Aza-BODIPY as a basic framework in biological imaging and organic electronic materials.
The invention will be described in detail below by way of examples. In the following examples, the compounds represented by the formula 1-1, the compounds represented by the formula 3-1 are described in the literature "Sheng, w.; zheng, y; wu, q.; wu, y; yu, c.; hao, e.; jiao, l.; wang, j.; pei, j.; prepared by the method described in Synthesis, properties, and Semiconducting Characteristics of BF, compounds of beta, beta-bispentanthrene-Fused Azadipyrromethenes, org. Lett.2017,19,2893-2896.
The chemical reagents (liquid bromine, N-bromosuccinimide, iodine, iodic acid, glacial acetic acid, tetraphenylpalladium phosphate, 9-dioctylfluorene-2, 7-bis (pinacolato borate), 9-dioctylfluorene-2, 7-bisboric acid, sodium carbonate, sodium chloride, anhydrous ferric trichloride, methylene chloride, chloroform, tetrahydrofuran, toluene, N-hexane) were all analytically pure reagents, unless otherwise specified, and were generally used without further treatment.
The reaction was followed using a 0.25 mm thick fluorescent TLC plate and a ZF-1 type three-way ultraviolet analyzer. 1H NMR and 13C NMR were performed using Bruker AVANCE III Spectrometers 300MHz,400MHz or 500MHz NMR, and the solvent was CDCl3. Mass spectrometry was performed using Bruker Apex IV Fourier Transform Ion Cyclotron Resonance Mass Spectrometer. The absorption spectrum used was an ultraviolet spectrophotometer type UV-2450, the fluorescence spectrum used was Edinburgh instruments FLS, the fluorescence quantum yield used was 1, 7-diphenyl-3, 5-di-p-methoxyphenyl azaBODIPY (chloroform, Φ=0.36) and indocyanine green (ICG) (dimethylsulfoxide, Φ=0.12).
Preparation example 1
Preparation of the compound represented by formula 1-2:
the compound represented by formula S1 is described in literature "Other SourcesBy Ahipa, t.n.; prepared by the method described in Adhikari, airody Vasudiva. Synthesis and mesomorphism of new 2-methoxy-3-cyanomatridine mesogens. Proceedings of SPIE, page 2012 8279,827915"827915-2.
Placing a compound shown as a formula S1, nitromethane and diethylamine in ethanol, and reacting for 12 hours at 65 ℃ to prepare a compound shown as a formula S2; the dosage ratio of the compound shown in the formula S1 to nitromethane, diethylamine and ethanol is 1mmol:8mmol:8mmol:10mL;
characterization data for compounds of formula S2 are: 1 H NMR(300MHz,CDCl 3 )δ7.88(d,J＝8.7Hz,2H),7.17(d,J＝8.4Hz,2H),6.90(d,J＝8.7Hz,2H),6.83(d,J＝8.5Hz,2H),4.82-4.76(m,1H),4.66-4.59(m,1H),4.20-4.09(m,1H),4.00(t,J＝6.5Hz,2H),3.90(t,J＝6.5Hz,2H),3.36-3.32(m,2H),1.84-1.70(m,4H),1.45-1.21(m,36H),0.92-0.80(m,6H). 13 C NMR(75MHz,CDCl 3 )δ195.46,163.44,158.63,130.91,130.33,129.26,128.44,114.91,114.29,79.93,68.32,67.98,41.27,38.80,31.92,29.64,29.36,26.05,25.96,22.70,14.13.HRMS(APCI)Calcd.for C 40 H 64 NO 5 [M+H] + :638.4780,found 638.4760.
placing a compound shown in a formula S2 and ammonium acetate into ethanol, and reacting at 65 ℃ for 24 hours, wherein the dosage ratio of the compound shown in the formula S2 to the ammonium acetate to the triethylamine to the boron trifluoride diethyl ether to the ethanol is 1mmol:15mmol:25mmol:25mmol:10mL; purifying to obtain a compound shown as a formula 1-2;
characterization data for compounds of formulas 1-2 are: 1 H NMR(300MHz,CDCl 3 )δ8.04(d,J＝8.9Hz,8H),6.97(d,J＝9.0Hz,8H),6.92(s,2H),4.06-4.00(m,8H),1.86-1.78(m,8H),1.44–1.26(m,72H),0.88(t,J＝6.6Hz,12H). 13 C NMR(75MHz,CDCl 3 )δ161.34,160.28,157.71,145.14,142.64,131.47,130.71,128.29,125.3,124.17,116.97,114.61,68.16,31.94,30.33,29.65,29.47,29.38,29.31,29.22,26.09,22.71,14.13.MS(MALDI)Calcd.for C 80 H 118 BF 2 N 3 O 4 [M] + :1233.9191,found 1233.9194.
example 1
a. A compound represented by the formula 1-1 was reacted with N-bromosuccinimide according to 1: mixing the mixture in methylene dichloride according to the molar ratio of 0.9, and carrying out contact reaction for 1h at the temperature of 0 ℃ to prepare a compound shown as a formula 2-1;
b. A compound shown as a formula 1-1 and liquid bromine are mixed according to a formula 1: mixing the mixture in methylene dichloride according to the molar ratio of 1.8, and carrying out contact reaction for 2 hours at the temperature of 0 ℃ to prepare a compound shown as a formula 3-1;
c. mixing a compound shown as a formula 2-1 with p-tert-butylphenylboronic acid, tetraphenylphosphine palladium and sodium carbonate in toluene, and carrying out contact reaction for 36h at 90 ℃ to obtain a compound shown as a formula 4-1; wherein the molar ratio of the compound shown in the formula 2-1 to the p-tert-butylphenylboronic acid, the tetraphenylphosphine palladium and the sodium carbonate is 1:1:0.05:2;
d. the compound shown as the formula 4-1 and N-bromosuccinimide are mixed according to the following formula 1: mixing the mixture in methylene dichloride according to the molar ratio of 0.9, and carrying out contact reaction for 1h at 25 ℃ to prepare a compound shown as a formula 5-1;
e. dispersing a compound shown in a formula 3-1, 9-dioctylfluorene-2, 7-bis (pinacolato borate), tetraphenylphosphine palladium and sodium carbonate in toluene, and carrying out contact reaction at 90 ℃ for 36 hours to obtain the compound shown in the formula 9-1; wherein the mol ratio of the compound shown in the formula 3-1 to 9, 9-dioctylfluorene-2, 7-bis (pinacolato borate), tetraphenylphosphine palladium and sodium carbonate is 1:2:0.05:2;
f. a compound shown as a formula 9-1 and anhydrous ferric trichloride are mixed according to a formula 1:10 in methylene dichloride, and carrying out oxidation reaction for 15min at 25 ℃ to obtain a compound shown as a formula I-1;
g. Dispersing a compound shown in a formula 5-1, 9-dioctylfluorene-2, 7-bis (pinacolato borate), tetraphenylphosphine palladium and sodium carbonate in toluene, and carrying out contact reaction at 90 ℃ for 36 hours to obtain the compound shown in the formula 10-1; wherein the mol ratio of the compound shown in the formula 5-1 to 9, 9-dioctylfluorene-2, 7-bis (pinacolato borate), tetraphenylphosphine palladium and sodium carbonate is 1:0.5:0.05:2;
h. a compound shown as a formula 10-1 and anhydrous ferric trichloride are mixed according to a formula 1:20 in a molar ratio in methylene dichloride, and carrying out oxidation reaction for 15min at 25 ℃ to obtain a compound shown as a formula II-1;
i. mixing a compound shown in a formula 2-1 with 9, 9-dioctylfluorene-2, 7-bis (pinacolato borate), tetraphenylphosphine palladium and sodium carbonate in toluene, and carrying out contact reaction at 90 ℃ for 36h to obtain a compound shown in a formula 10-1; wherein the mol ratio of the compound shown in the formula 11-1 to 9, 9-dioctylfluorene-2, 7-bis (pinacolato borate), tetraphenylphosphine palladium and sodium carbonate is 1:0.5:0.05:2;
j. a compound represented by the formula 11-1 was reacted with liquid bromine according to 1: mixing the mixture in methylene dichloride according to a molar ratio of 1.8, and carrying out contact reaction for 2 hours at 0 ℃ to prepare a compound shown as a formula 12-1;
k. A compound represented by the formula 11-1, iodic acid and iodine were mixed according to 1:4:4 in the presence of dichloromethane and glacial acetic acid at 45 ℃ for contact reaction for 2 hours to prepare a compound shown as a formula 12-2;
and l, mixing a compound shown as a formula 12-1 with anhydrous ferric trichloride according to a formula 1:10 in a molar ratio in trichloroethylene, and carrying out oxidation reaction at 25 ℃ for 15min to obtain a compound shown as a formula III-1;
m, mixing a compound shown as a formula 12-2 with ferric trichloride according to a formula 1:10 in methylene dichloride, and carrying out oxidation reaction for 15min at 25 ℃ to obtain the compound shown as the formula III-2.
In each of the above steps, the amount of the solvent used in each step was 10mL relative to 1mmol of the compound represented by the formula 1-1, the formula 2-1, the formula 3-1, the formula 4-1, the formula 5-1, the formula 9-1, the formula 10-1, the formula 11-1, and the formula 12-1. The product characterization data for each of the above steps are as follows:
a compound represented by formula 2-1: 1 H NMR(300MHz,CDCl 3 )δ8.10-8.02(m,4H),7.91(d,J＝8.9,2H),7.76(d,J＝7.1Hz,2H),7.08-6.89(m,9H),3.92(d,J＝1.8Hz,3H),3.90-3.80(m,9H). 13 C NMR(101MHz,CDCl 3 )δ162.61,161.23,160.87,160.32,152.72,146.83,145.08,142.26,139.03,132.31,132.04,130.91,12.60,124.25,122.77,117.88,114.36,114.20,113.49,113.38,55.48,55.45,55.40,55.25.HRMS(APCI)Calcd.for C 36 H 30 BBrF 2 N 3 O 4 [M+H] + :696.1481,found 696.1468.
a compound represented by formula 4-1: 1 H NMR(400MHz,CDCl 3 )δ8.09(d,J＝9.0Hz,2H),8.03(d,J＝9.0Hz,2H),7.46-7.43(m,4H),7.19(d,J＝8.4Hz,2H),6.98-6.89(m,7H),6.85-6.73(m,4H),3.87-3.81(m,12H),1.28(s,9H). 13 C NMR(126MHz,CDCl 3 )δ161.90,160.80,160.46,159.72,158.92,156.70,149.96,145.97,144.45,143.22,139.59,132.56,132.41,131.59,130.73,130.22,125.11,116.95,114.18,114.10,113.25,113.13,55.40,55.26,55.15,34.53,31.32.HRMS(APCI)calcd.for C 46 H 43 BF 2 N 3 O 4 [M+H] + :750.3315,found 750.3311.
a compound represented by formula 5-1: 1 H NMR(300MHz,CDCl 3 )δ7.93(d,J＝8.70Hz,2H),7.74(d,J＝8.70Hz,2H),7.42(d,J＝8.31Hz,4H),7.43(m,4H),7.21(d,J＝8.19Hz,2H),7.03-6.98(m,4H),6.89(d,J＝8.13Hz,2H),6.78-6.74(m,4H),3.89(s,3H),3.86(s,3H),3.81(s,3H),3.79(s,3H),1.29(s,9H). 13 C NMR(75MHz,CDCl 3 )δ161.37,161.17,161.03,160.41,160.13,150.52,146.19,143.04,141.88,139.93,132.54,132.30,130.12,129.91,125.31,124.17,124.08,113.49,113.42,113.35,107.36,55.35,55.23,55.18,34.57,31.28.HRMS(APCI)calcd.for C 46 H 41 BBrF 2 N 3 O 4 [M+H] + :828.2414,found 828.2388.
a compound represented by formula 9-1: 1 H NMR(400MHz,CDCl 3 )δ7.88-7.66(m,2H),7.54(t,J＝8.1Hz,6H),7.44(d,J＝8.8Hz,4H),7.40-7.38(m,2H),7.32-7.26(m,4H),7.00-6.95(m,2H),6.95(s,2H),6.80-6.73(m,8H),3.80(s,6H),3.73(s,6H),1.25(s,12H). 13 C NMR(101MHz,CDCl 3 )δ160.57,159.71,157.99,153.66,153.32,145.14,139.59,138.72,137.76,132.39,132.29,129.24,126.82,125.17,122.45,119.78,119.66,113.10,55.08,54.98,46.36,26.61.HRMS(APCI)calcd.For C 66 H 55 BF 2 N 3 O 4 [M+H] + :1002.4248,found 1002.4267.
a compound of formula i-1: 1 H NMR(400MHz,CDCl 3 )δ9.48(d,J＝9.4Hz,1H),8.63(s,1H),8.15(s,1H),8.05(d,J＝2.6Hz,1H),7.89(d,J＝6.8Hz,1H),7.59(d,J＝8.7Hz,2H),7.45–7.41(m,1H),7.39–7.34(m,3H),7.02–6.98(m,2H),4.14(s,3H),3.96(s,3H),1.29(s,6H).HRMS(APCI)calcd.For C 66 H 51 BF 2 N 3 O 4 [M+H] + :998.3935,found 998.3958.
a compound represented by formula 10-1: 1 H NMR(300MHz,CDCl 3 )δ7.50-7.40(m,9H),7.20(d,J＝8.3Hz,2H),6.97-6.89(m,4H),6.81-6.70(m,8H),3.82(s,3H),3.78(d,J＝4.3Hz,6H),3.75(s,3H),1.55(s,5H),1.29(s,9H),1.16(s,6H),0.83(t,J＝6.8Hz,4H),0.42(s,2H). 13 C NMR(75MHz,CDCl 3 )δ171.70,161.43,160.60,158.46,151.84,150.93,145.89,140.57,133.34,133.24,131.18,131.02,130.23,125.99,125.55,124.08,120.63,114.02,113.96,56.03,55.93,55.81,41.05,32.69,32.11,30.89,30.42,30.25,24.70,23.47,14.90.MS(MALDI)Calcd.for C121H122B2F4N6O8[M] + :1885.9493,found 1885.9491.
a compound of formula ii-1: 1 H NMR(400MHz,CDCl 3 )δ9.42(s,4H),8.77(s,2H),8.32(s,2H),8.06(s,6H),7.96(s,2H),7.60(s,8H),7.35(s,6H),6.99(s,8H),4.07(s,12H),3.95(s,12H),1.14-1.06(m,28H),0.61-0.53(m,6H).MS(MALDI)Calcd.for C121H114B2F4N6O8[M] + :1877.8867,found 1877.8868.
a compound represented by formula 11-1: 1 H NMR(500MHz,CDCl 3 )δ8.11(d,J＝7.7Hz,4H),8.05(d,J＝7.9Hz,4H),7.47(d,J＝7.9Hz,10H),6.97-6.92(m,14H),6.80-6.75(m,8H),3.87(d,J＝8.5Hz,12H),3.79(d,J＝14.9Hz,12H),1.59(s,4H),1.22-1.15(m,12H),1.00(s,4H),0.90(d,J＝6.9Hz,4H),0.83(t,J＝6.8Hz,6H),0.42(s,4H). 13 C NMR(126MHz,CDCl 3 )δ161.98,160.86,159.77,159.14,156.42,154.23,150.99,149.12,146.10,144.36,143.37,139.72,132.69,132.48,131.65,130.77,129.42,125.24,124.90,124.08,123.44,119.74,117.08,114.22,114.14,113.28,113.16,55.54,55.41,55.17,55.04,54.83,40.25,31.91,30.11,29.63,29.46,23.90,22.69,14.12.HRMS(APCI)Calcd.for C 101 H 99 B 2 F 4 N 6 O 8 [M+H] + :1622.7675,found 1622.7689.
a compound represented by formula 12-1: 1 H NMR(300MHz,CDCl 3 )δ7.93(d,J＝8.6Hz,4H),7.76(d,J＝8.0Hz,4H),7.50-7.43(m,10H),7.01(t,J＝7.9Hz,8H),6.92(d,J＝6.5Hz,4H),6.71(d,J＝8.5Hz,8H),3.88(d,J＝10.4Hz,12H),3.76(d,J＝6.8Hz,12H),1.57(s,4H),1.13(s,12H),0.95(s,8H),0.82(t,J＝6.6Hz,6H),0.38(s,4H). 13 C NMR(126MHz,CDCl 3 )δ161.20,161.13,160.92,160.49,160.19,154.50,151.19,145.96,143.35,141.70,140.17,139.99,132.48,132.35,129.36,125.02,124.11,122.60,120.03,113.54,113.46,113.38,107.59,55.39,55.26,55.15,55.08,54.92,40.20,31.88,30.06,29.60,29.43,23.90,22.66,14.09.HRMS(APCI)Calcd.for C 101 H 97 B 2 Br 2 F 4 N 6 O 8 [M+H] + :1779.5831,found 1779.5847.
a compound represented by formula 12-2: 1 H NMR(300MHz,CDCl 3 )δ7.86(d,J＝8.5Hz,4H),7.68(d,J＝8.4Hz,4H),7.49-7.40(m,10H),7.00(t,J＝9.4Hz,8H),6.91(d,J＝6.2Hz,4H),6.69(d,J＝8.5Hz,8H),3.88(d,J＝10.5Hz,12H),3.75(d,J＝6.2Hz,12H),1.56(s,4H),1.13(s,12H),0.95(s,8H),0.81(d,J＝7.1Hz,6H),0.38(s,4H). 13 C NMR(101MHz,CDCl 3 )δ161.18,160.97,160.44,160.14,157.34,151.16,145.94,144.08,141.80,139.96,132.45,132.35,125.14,124.96,124.05,124.03,122.54,122.02,113.37,113.32,113.28,55.37,55.23,55.13,55.07,54.89,4018,31.86,30.03,29.59,29.43,2.88,22.66,14.10.HRMS(APCI)Calcd.for C 101 H 97 B 2 F 4 I 2 N 6 O 8 [M+H] + :1874.5608,found 1874.5618.
A compound of formula iii-1: 1 H NMR(300MHz,CDCl 3 )δ9.09(d,J＝9.4Hz,2H),8.73(s,2H),8.11(s,2H),8.00-7.80(m,10H),7.59(d,J＝8.0Hz,4H),7.20(d,J＝8.3Hz,2H),7.11(d,J＝8.2Hz,4H),7.02(d,J＝8.0Hz,4H),6.95(d,J＝8.4Hz,4H),4.11(s,6H),3.95(s,12H),3.89(s,6H),1.57(s,4H),1.11(s,12H),0.99(s,8H),0.77(s,6H),0.52(s,4H).HRMS(APCI)Calcd.for C 101 H 93 B 2 Br 2 F 4 N 6 O 8 [M+H] + :1775.5518,found 1775.5540.
a compound of formula iii-2: 1 H NMR(300MHz,CDCl 3 )δ9.07(d,J＝9.1Hz,2H),8.71(s,2H),8.11(s,2H),7.98(s,2H),7.86(d,J＝8.7Hz,4H),7.79(d,J＝8.4Hz,4H),7.58(d,J＝8.5Hz,4H),7.20(d,J＝9.4Hz,2H),7.10(d,J＝8.7Hz,4H),7.12-6.95(m,8H),4.11(s,6H),3.96(t,J＝7.4Hz,12H),3.90(s,6H),1.56-1.51(m,4H),1.11(s,12H),0.99(s,8H),0.77(t,J＝6.8Hz,6H),0.52(s,4H).HRMS(APCI)Calcd.for C 101 H 93 B 2 F 4 I 2 N 6 O 8 [M+H] + :1869.5261,found 1869.5280.
example 2
a. The compound shown as the formula 1-2 and N-bromosuccinimide are mixed according to the formula 1: mixing the mixture in methylene dichloride according to the molar ratio of 0.9, and carrying out contact reaction for 1h at the temperature of 0 ℃ to prepare a compound shown as a formula 2-2;
b. a compound shown as a formula 1-2 and liquid bromine are mixed according to a formula 1: mixing the mixture in methylene dichloride according to a molar ratio of 1.8, and carrying out contact reaction for 2 hours at 0 ℃ to prepare a compound shown as a formula 3-2;
c. mixing a compound shown as a formula 2-2 with p-tert-butylphenylboronic acid, tetraphenylphosphine palladium and sodium carbonate in toluene, and carrying out contact reaction for 36h at 90 ℃ to obtain a compound shown as a formula 4-2; wherein the mol ratio of the compound shown in the formula 2-2 to the p-tert-butylphenylboronic acid, the tetraphenylphosphine palladium and the carbonate is 1:1:0.05:2;
d. the compound shown as the formula 4-2 and N-bromosuccinimide are mixed according to the following formula 1: mixing the mixture in methylene dichloride according to the molar ratio of 0.9, and carrying out contact reaction for 1h at 25 ℃ to prepare a compound shown as a formula 5-2);
e. mixing a compound shown in a formula 3-2 with 9, 9-dioctylfluorene-2, 7-bis (pinacolato borate), tetraphenylphosphine palladium and sodium carbonate in toluene, and carrying out contact reaction for 36h at 90 ℃ to obtain the compound shown in the formula 9-2; wherein the mol ratio of the compound shown in the formula 3-2 to 9, 9-dioctylfluorene-2, 7-bis (pinacolato borate), tetraphenylphosphine palladium and carbonate is 1:2:0.05:2;
f. A compound shown as a formula 9-2 and anhydrous ferric trichloride are mixed according to a formula 1:10 in methylene dichloride, and carrying out oxidation reaction for 15min at 25 ℃ to obtain a compound shown as a formula I-2;
g. carrying out contact reaction on a compound shown in a formula 5-2, 9-dioctylfluorene-2, 7-bis (pinacolato borate), tetraphenylphosphine palladium and sodium carbonate in toluene at 90 ℃ for 36 hours to obtain the compound shown in the formula 10-2; wherein the mol ratio of the compound shown in the formula 5-2 to 9, 9-dioctylfluorene-2, 7-bis (pinacolato borate), tetraphenylphosphine palladium and sodium carbonate is 1:0.5:0.05:2;
h. a compound shown as a formula 10-2 and anhydrous ferric trichloride are mixed according to a formula 1:20 in a molar ratio in methylene dichloride, and carrying out oxidation reaction for 15min at 25 ℃ to obtain a compound shown as a formula II-2;
in each of the above steps, the amount of the solvent used in each step was 10mL relative to 1mmol of the compound represented by the formula 1-2, the formula 2-2, the formula 3-2, the formula 4-2, the formula 5-2, the formula 9-2, and the formula 10-2. The product characterization data for each of the above steps are as follows:
a compound of formula 1-2: 1 H NMR(300MHz,CDCl 3 )δ8.04(d,J＝8.9Hz,8H),6.97(d,J＝9.0Hz,8H),6.92(s,2H),4.06-4.00(m,8H),1.86-1.78(m,8H),1.44–1.26(m,72H),0.88(t,J＝6.6Hz,12H). 13 C NMR(75MHz,CDCl 3 )δ161.34,160.28,157.71,145.14,142.64,131.47,130.71,128.29,125.3,124.17,116.97,114.61,68.16,31.94,30.33,29.65,29.47,29.38,29.31,29.22,26.09,22.71,14.13.MS(MALDI)Calcd.for C 80 H 118 BF 2 N 3 O 4 [M] + :1233.9191,found 1233.9194.
a compound represented by formula 2-2: δ8.04 (t, j=8.0 hz, 4H), 7.89 (d, j=8.8 hz, 2H), 7.74 (d, j=8.7 hz, 2H), 7.05-6.89 (m, 9H), 4.11-3.98 (m, 8H), 1.88-1.76 (m, 8H), 1.47-1.26 (m, 72H), 0.88 (t, j=6.6 hz, 12H). 13 C NMR(101MHz,CDCl 3 )δ162.28,160.85,160.54,159.91,152.69,146.87,145.08,144.30,139.11,132.28,132.05,130.88,124.43,123.14,114.80,114.71,114.02,113.78,68.24,68.16,67.94,31.94,29.69,29.66,29.61,29.43,29.37,29.29,29.23,29.11,26.11,26.05,25.99,22.71,14.14.MS(MALDI)Calcd.for C 80 H 117 BBrF 2 N 3 O 4 [M] + :1313.8271,found 1313.8270.
A compound represented by formula 3-2: 1 H NMR(300MHz,CDCl 3 )δ7.88(d,J＝8.7Hz,4H),7.73(d,J＝8.7Hz,4H),6.98-6.94(m,8H),4.05-3.97(m,8H),1.87-1.74(m,8H),1.46-1.27(m,72H),0.87(d,J＝6.8Hz,12H). 13 C NMR(75MHz,CDCl 3 )δ161.24,160.43,157.13,144.02,141.95,132.45,123.36,121.79,114.10,113.94,108.55,68.15,68.03,32.01,29.74,29.52,29.46,29.30,26.15,22.77,14.20.MS(MALDI)Calcd.for C 80 H 116 BBr 2 F 2 N 3 O 4 [M] + :1391.7373,found 1391.7390.
a compound represented by formula 4-2: 1 H NMR(400MHz,CDCl 3 )δ8.09(d,J＝8.9Hz,2H),8.02(d,J＝8.9Hz,2H),7.45-7.41(m,4H),7.18(d,J＝8.4Hz,2H),6.97-6.89(m,7H),6.85-6.79(m,2H),6.76(d,J＝8.9Hz,2H),4.05-3.93(m,8H),1.85-1.75(m,8H),1.46-1.27(m,81H),0.88(t,J＝6.2Hz,12H). 13 C NMR(101MHz,CDCl 3 )δ161.35,160.37,160.09,159.29,158.86,156.60,149.83,145.95,144.42,143.16,139.56,132.53,132.41,131.56,130.69,130.25,125.08,116.81,114.62,113.72,113.56,68.14,68.00,67.89,34.52,31.94,31.33,29.65,29.62,29.48,29.45,29.37,29.28,29.17,26.12,26.08,26.03,22.70,14.13.MS(MALDI)Calcd.for C 90 H 130 BF 2 N 3 O 4 [M] + :1366.0131,found 1366.0135.
a compound represented by formula 5-2: 1 H NMR(400MHz,CDCl 3 )δ7.90(d,J＝8.9Hz,2H),7.72(d,J＝8.8Hz,2H),7.42-7.37(m,4H),7.20(d,J＝8.5Hz,2H),7.00-6.95(m,4H),6.88(d,J＝8.4Hz,2H),6.73(t,J＝8.5Hz,4H),4.05-3.98(m,4H),3.95-3.89(m,4H),1.85-1.71(m,8H),1.46(d,J＝5.6Hz,8H),1.27(d,J＝4.7Hz,73H),0.88(t,J＝6.8Hz,12H). 13 C NMR(101MHz,CDCl 3 )δ161.28,160.82,160.68,159.99,159.70,150.70,146.17,142.99,141.88,139.88,132.53,132.28,130.15,130.04,125.30,123.98,123.88,122.36,114.00,113.82,113.67,68.13,67.96,34.57,31.94,31.30,29.66,29.64,29.57,29.46,29.41,29.37,29.28,29.20,26.09,26.04,22.70,14.13.MS(MALDI)Calcd.for C 90 H 129 BBrF 2 N 3 O 4 [M] + :1445.9211,found 1445.9209.
a compound represented by formula 9-2: 1 H NMR(400MHz,CDCl 3 )δ7.72(d,J＝6.8Hz,1H),7.66(t,J＝6.7Hz,2H),7.55-7.37(m,12H),7.35–7.28(m,4H),7.18(dd,J＝7.8,1.3Hz,1H),6.99(d,J＝7.8Hz,1H),6.95(s,1H),6.84–6.67(m,8H),3.96–3.85(m,8H),1.81–1.68(m,8H),1.26(s,72H),0.88(t,J＝6.2Hz,12H). 13 C NMR(101MHz,CDCl 3 )δ160.40,160.08,159.46,158.33,158.15,153.90,153.86,153.73,153.45,149.24,145.25,132.55,132.46,132.34,130.28,129.46,127.22,126.98,122.65,122.60,119.95,114.36,113.84,113.71,113.49,68.13,68.03,67.91,67.85,58.49,46.73,46.53,31.93,29.70,29.66,29.64,29.61,29.58,29.46,29.43,29.37,,26.93,26.81,26.09,26.07,26.00,22.70,18.45,14.13.HRMS(APCI)calcd.For C 110 H 143 BF 2 N 3 O 4 [M+H] + :1619.1134,found 1619.1146.
a compound of formula I-2: 1 H NMR(400MHz,CDCl 3 )δ9.39(d,J＝9.5Hz,2H),8.48(s,2H),8.02(s,2H),7.87(s,2H),7.80-7.78(m,2H),7.35-7.33(m,6H),7.25-7.17(m,6H),6.84(d,J＝8.4Hz,4H),4.24(t,J＝6.3Hz,4H),3.99(t,J＝6.5Hz,4H),1.97-1.88(m,4H),1.84-1.77(m,4H),1.58(d,J＝6.5Hz,4H),1.47-1.01(m,100H). 13 C NMR(101MHz,CDCl 3 )δ161.62,159.65,153.87,152.87,150.72,148.61,138.86,138.24,138.17,137.56,132.93,127.97,127.57,127.30,127.14,126.58,125.41,124.39,124.00,123.49,122.66,120.29,119.34,117.07,115.63,114.72,113.80,108.84,68.39,68.27,46.63,31.99,30.16,29.75,29.67,29.63,29.51,29.44,27.44,26.32,26.22,22.74,14.16.HRMS(APCI)calcd.For C 110 H 139 BF 2 N 3 O 4 [M+H] + :1615.0821,found 1615.0811.
a compound represented by formula 10-2: 1 H NMR(500MHz,CDCl 3 )δ7.48-7.39(m,9H),7.20(d,J＝8.1Hz,2H),6.98-6.87(m,4H),6.83-6.61(m,8H),3.97-3.88(m,8H),1.85-1.66(m,9H),1.57(d,J＝25.2Hz,5H),1.49-1.06(m,91H),1.04-0.73(m,22H),0.42(s,2H). 13 C NMR(126MHz,CDCl 3 )δ160.31,159.44,159.41,158.41,157.70,157.70,151.02,150.05,145.32,145.14,140.27,139.95,139.81,132.87,132.55,132.46,130.29,125.18,124.63,124.55,123.11,113.74,113.62,68.01,67.93,67.83,54.93,40.26,31.94,31.34,29.67,29.65,29.48,29.37,26.12,26.08,22.70,14.11.MS(MALDI)Calcd.for C 209 H 298 B 2 F 4 N 6 O 8 [M] + :3120.3301,found 3120.3302.
a compound of formula ii-2: 1 H NMR(300MHz,CDCl 3 )δ9.43(d,J＝9.0Hz,4H),8.79(s,2H),8.32(s,2H),8.11(d,J＝9.3Hz,6H),7.94(s,2H),7.64-7.57(m,8H),7.35(d,J＝8.7Hz,6H),7.05-6.89(m,8H),4.24(d,J＝6.0Hz,8H),4.08(t,J＝6.2Hz,8H),1.90(d,J＝5.8Hz,15H),1.69-1.21(m,148H),1.07(d,J＝29.2Hz,20H),0.95-0.83(m,19H),0.77(t,J＝6.6Hz,6H),0.57(s,5H). 13 C NMR(126MHz,CDCl 3 )δ161.56,161.49,159.76,150.63,149.49,148.86,148.73,140.00,138.11,137.90,137.71,132.80,132.13,128.46,127.53,127.01,126.17,125.79,125.46,125.24,120.29,119.74,117.49,117.05,115.61,115.17,114.80,114.04,109.27,109.09,68.41,68.28,54.80,40.73,32.09,31.56,29.87,29.77,29.64,29.55,26.39,22.83,22.71,14.23,14.15.MS(MALDI)Calcd.for C 209 H 290 B 2 F 4 N 6 O 8 [M] + :3112.2675,found 3112.2677.
test example 1
1mg of the compound represented by the formula II-1 is weighed and dissolved in 2mL of chloroform, and then diluted with toluene, chloroform and tetrahydrofuran respectively to prepare the compound with the molar concentration of 10 -6 A mol/L solution; respectively carrying out absorption spectrum test and emission spectrum test, wherein the absorption and emission spectrum test result is shown in figure 1 (the left side of the figure is an absorption spectrum diagram, and the right side is an emission spectrum diagram); the excitation wavelength was 808nm.
As can be seen from FIG. 1, the maximum absorption peak of the compound II-1 can reach 840nm, the maximum emission peak can reach 870nm, and the compound II-1 reaches near infrared region, and has higher photoelectric conversion efficiency and wider application prospect when being applied as an organic optical material.
Test example 2
1mg of the compound represented by the formula II-2 is weighed and dissolved in 2mL of chloroform, and then diluted with toluene, chloroform and tetrahydrofuran respectively to prepare the compound with the molar concentration of 10 -6 A mol/L solution; respectively carrying out absorption spectrum test and emission spectrum test, wherein the absorption and emission spectrum test results are shown in figure 2 (the left side of the figure is an absorption spectrum diagram, and the right side is an emission spectrum diagram); the excitation wavelength was 808nm.
As shown in FIG. 2, the maximum absorption peak of the compound II-2 can reach 840nm, the maximum emission peak can reach 870nm, the compound II-2 reaches near infrared region, the solubility of the alkyl long chain is effectively improved, the compound II-2 is easy to prepare when being applied as an organic optical material, the photoelectric conversion efficiency is higher, and the application prospect is wider.
Test example 3
1mg of the compound represented by the formula III-1 is weighed and dissolved in 2mL of chloroform, and then diluted with toluene, chloroform and tetrahydrofuran respectively to prepare the compound with the molar concentration of 10 -6 A mol/L solution; respectively carrying out absorption spectrum test and emission spectrum test, wherein the absorption and emission spectrum test result is shown in figure 3 (the left side of the figure is an absorption spectrum diagram, and the right side is an emission spectrum diagram); the excitation wavelength was 730nm.
As can be seen from FIG. 3, the absorption peak position of the compound III-1 is located in the near infrared region, the maximum absorption peak position is near 800nm, the maximum emission peak is 850nm, and the compound III-1 has less damage to organisms and strong penetrability in biological application.
Test example 4
1mg of the compound represented by the formula III-2 is weighed and dissolved in 2mL of chloroform, and then diluted with toluene, chloroform and tetrahydrofuran respectively to prepare the compound with the molar concentration of 10 -6 A mol/L solution; the absorption spectrum and the emission spectrum are respectively tested, and the test result of the absorption and the emission spectrum is shown in figure 4 (the left side of the figure is an absorption spectrum diagram, and the right side is an emission spectrum diagram); the excitation wavelength was 730nm.
As can be seen from FIG. 4, the absorption peak position of the compound III-2 is located in the near infrared region, the maximum absorption peak position is near 800nm, the maximum emission peak is 850nm, and the compound III-2 has less damage to organisms and strong penetrability in biological application.
Test example 5
1mg of a compound represented by the formula III-1, III-2 was weighed and dissolved in 2mL of toluene as a sample solution to be measured, followed by a singlet oxygen test.
The singlet oxygen test is carried out by taking 1, 3-diphenyl benzofuran (DPBF) as capturing agent, and configuring DPBF concentration to be 4×10 by ultraviolet spectrophotometry -5 mol/L, sample concentrationIs 1X 10 -5 mol/L, capturing agent DPBF is added into a sample solution to be detected and placed at 660nm wavelength, and P=0.5 mW/cm 2 Irradiation at intensity for the same time, quantum yield of singlet oxygen formation (Φ) was calculated by a relative method using optically matched solution Δ ) The specific results are shown in FIG. 5, wherein the left half of the graph represents the degradation curve of DPBF for III-1 and the right half represents the degradation curve for DPBF for III-2. And comparing the photooxidation quantum yield of the target dye sensitized DPBF with the quantum yield of 2, 6-dibromo-3, 5- (4-methoxy) benzene-1, 7-phenylazabodipy (standard substance, denoted as "S"). Standard DPBF singlet oxygen yield in toluene Φ Δ =0.77. The singlet oxygen yield of III-1 was measured to be 6% and the singlet oxygen yield of III-2 was measured to be 37%.
As shown in FIG. 5, the compounds III-1 and III-2 have strong singlet oxygen efficiency, and have strong penetrability to organisms and less damage due to absorption in the near infrared region, are not easy to be subjected to photolysis, have high utilization rate, and have wide application prospects in economic and environmental protection.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (26)
1. An organic conjugated molecular material taking dibenzofuran Aza-BODIPY as a basic framework is characterized in that the structure of the organic conjugated molecular material is shown as a formula I, a formula II or a formula III,
wherein R1, R2, R3 and R4 are each independently selected from methoxy or n-dodecyloxy, R5 is tert-butyl, R6 and R7 are both methyl or n-octyl, and X is bromine or iodine;
m, n1, n2, n3 and n4 are all 1.
2. The organic conjugated molecular material of basic skeleton according to claim 1, wherein the structure of the organic conjugated molecular material is shown as formula I-1, formula I-2, formula II-1, formula II-2, formula III-1 or formula III-2,
wherein C in the formula 8 H 17 Is n-octyl, C 12 H 25 O is n-dodecyloxy.
3. A method for preparing the organic conjugated molecular material with the structure shown in the formula I in claim 1, which comprises the following steps:
1) Under alkaline conditions, carrying out a first contact reaction on a compound with a structure shown in a formula 3, a fluorenyl boric acid compound and a palladium catalyst in a solvent to obtain a compound with a structure shown in a formula 9;
2) Carrying out a first oxidation reaction on a compound with a structure shown in a formula 9 and an oxidant in a solvent to prepare an organic conjugated molecular material with a structure shown in a formula I,
Wherein R1, R2, R3 and R4 in the formula are respectively and independently selected from methoxy or n-dodecyloxy, and X is bromine or iodine; n1, n2, n3 and n4 are all 1;
the structure of the compound with the structure shown in the formula 3 is shown in the formula 3-1 or the formula 3-2,
the fluorenyl boric acid compound is 9, 9-dioctyl fluorene-2, 7-bisboric acid or 9, 9-dioctyl fluorene-2, 7-bis (pinacolato borate);
the palladium catalyst is selected from at least one of tetraphenylphosphine palladium, palladium acetate, palladium chloride, bis (triphenylphosphine) palladium dichloride and tris (dibenzylideneacetone) dipalladium;
in step 2), the oxidizing agent is at least one selected from the group consisting of anhydrous ferric trichloride, molybdenum pentachloride and dichlorodicyanobenzoquinone.
4. The preparation method according to claim 3, wherein in the step 1), the compound having the structure shown in formula 3, the fluorenylboronic acid compound and the palladium catalyst are used in a molar ratio of 1:2-4:0.05-0.1.
5. A production method according to claim 3, wherein the first contact reaction satisfies at least the following conditions: the reaction temperature is 90-120 ℃ and the reaction time is 24-36h
6. The preparation method according to claim 3, wherein in the step 1), the pH of the reaction system is controlled by carbonate, and the molar ratio of the compound having the structure shown in formula 3 to the carbonate is 1:2-6.
7. The production method according to claim 6, wherein the carbonate is at least one selected from the group consisting of sodium carbonate, potassium carbonate and cesium carbonate.
8. The preparation method according to claim 3, wherein in the step 2), the compound having the structure shown in formula 9 and the oxidizing agent are used in a molar ratio of 1:4-15.
9. A production method according to claim 3, wherein in step 2), the first oxidation reaction satisfies at least the following conditions: the reaction temperature is 0-45 ℃ and the reaction time is 10-30min.
10. A method for preparing the organic conjugated molecular material with the structure shown in the formula II in claim 1, which comprises the following steps:
1) Under alkaline conditions, carrying out a second contact reaction on a compound with a structure shown in a formula 5, a fluorenyl boric acid compound and a palladium catalyst in a solvent to obtain a compound with a structure shown in a formula 10;
2) Carrying out a second oxidation reaction on a compound with a structure shown in a formula 10 and an oxidant in a solvent to prepare an organic conjugated molecular material with a structure shown in a formula II;
wherein R1, R2, R3 and R4 in the formula are respectively and independently selected from methoxy or n-dodecyloxy, R5 is tert-butyl, R6 and R7 are methyl or n-octyl, and X is bromine or iodine; m, n1, n2, n3 and n4 are all 1;
Wherein the structure of the compound with the structure shown in the formula 5 is shown in the formula 5-1 or the formula 5-2,
the fluorenyl boric acid compound is 9, 9-dioctyl fluorene-2, 7-bisboric acid or 9, 9-dioctyl fluorene-2, 7-bis (pinacolato borate);
the palladium catalyst is selected from at least one of tetraphenylphosphine palladium, palladium acetate, palladium chloride, bis (triphenylphosphine) palladium dichloride and tris (dibenzylideneacetone) dipalladium;
the oxidant is at least one selected from anhydrous ferric trichloride, molybdenum pentachloride and dichlorodicyanobenzoquinone.
11. The preparation method according to claim 10, wherein in step 1), the compound having the structure shown in formula 5, the fluorenylboronic acid compound and the palladium catalyst are used in a molar ratio of 1:0.4-0.6:0.05-0.1.
12. The production method according to claim 10, wherein in step 1), the second contact reaction satisfies at least the following conditions: the reaction temperature is 90-120 ℃ and the reaction time is 24-36h.
13. The preparation method according to claim 10, wherein in step 1), the pH of the reaction system is controlled by carbonate, and the molar ratio of the compound having the structure shown in formula 5 to carbonate is 1:2-6.
14. The production method according to claim 13, wherein the carbonate is at least one selected from sodium carbonate, potassium carbonate and cesium carbonate.
15. The preparation method according to claim 10, wherein in step 2), the compound having the structure shown in formula 10 and the oxidant are used in a molar ratio of 1:4-15.
16. The production method according to claim 10, wherein in step 2), the second oxidation reaction satisfies at least the following conditions: the reaction temperature is 0-45 ℃ and the reaction time is 10-30min.
17. A method for preparing the organic conjugated molecular material with the structure shown in the formula III according to claim 1, wherein the preparation method comprises the following steps:
1) Under alkaline conditions, carrying out a third contact reaction on a compound with a structure shown in a formula 2, a fluorenyl boric acid compound and a palladium catalyst in a solvent to obtain a compound with a structure shown in a formula 11;
2) Carrying out a fourth contact reaction on a compound with a structure shown in a formula 11 and halogen source in a solvent to prepare an organic conjugated molecular material with a structure shown in a formula 12;
3) Carrying out a third oxidation reaction on a compound with a structure shown in a formula 12 and an oxidant in a solvent to prepare an organic conjugated molecular material with a structure shown in a formula II;
Wherein R1, R2, R3 and R4 in the formula are respectively and independently selected from methoxy or n-dodecyloxy, R5 is tert-butyl, R6 and R7 are methyl or n-octyl, and X is bromine or iodine; m, n1, n2, n3 and n4 are all 1;
wherein the structure of the compound with the structure shown in the formula 2 is shown in the formula 2-1 or the formula 2-2,
the fluorenyl boric acid compound is 9, 9-dioctyl fluorene-2, 7-bisboric acid or 9, 9-dioctyl fluorene-2, 7-bis (pinacolato borate);
the palladium catalyst is selected from at least one of tetraphenylphosphine palladium, palladium acetate, palladium chloride, bis (triphenylphosphine) palladium dichloride and tris (dibenzylideneacetone) dipalladium;
the halogen source is selected from at least one of liquid bromine, N-bromosuccinimide and iodine simple substance;
the oxidant is at least one selected from anhydrous ferric trichloride, molybdenum pentachloride and dichlorodicyanobenzoquinone.
18. The preparation method according to claim 17, wherein in the step 1), the compound having the structure shown in formula 2, the fluorenylboronic acid compound and the palladium catalyst are used in a molar ratio of 1:0.4-0.6:0.05-0.1.
19. The production method according to claim 17, wherein in step 1), the third contact reaction satisfies at least the following conditions: the reaction temperature is 90-120 ℃ and the reaction time is 24-36h.
20. The preparation method according to claim 17, wherein in step 1), the pH of the reaction system is controlled by carbonate, and the molar ratio of the compound having the structure shown in formula 2 to carbonate is 1:2-6.
21. The production method according to claim 20, wherein the carbonate is at least one selected from sodium carbonate, potassium carbonate and cesium carbonate.
22. The process according to claim 17, wherein in step 2), the molar ratio of the compound having the structure represented by formula 11 to the halogen source is 1:1.8-2.4.
23. The production method according to claim 17, wherein in step 2), the fourth contact reaction satisfies at least the following conditions: the reaction temperature is 0-45 ℃ and the reaction time is 1-6h.
24. The preparation method according to claim 17, wherein in the step 3), the compound having the structure shown in formula 12 and the oxidizing agent are used in a molar ratio of 1:4-15.
25. The production method according to claim 17, wherein in step 3), the third oxidation reaction satisfies at least the following conditions: the reaction temperature is 0-45 ℃ and the reaction time is 10-30min.
26. Use of the organic conjugated molecular material with bifluorene Aza-BODIPY as basic skeleton according to claim 1 or 2 in biological imaging and organic electronic materials.
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