CN118005601A - Compound with aggregation-induced emission performance and preparation method thereof - Google Patents
Compound with aggregation-induced emission performance and preparation method thereof Download PDFInfo
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- CN118005601A CN118005601A CN202410013312.XA CN202410013312A CN118005601A CN 118005601 A CN118005601 A CN 118005601A CN 202410013312 A CN202410013312 A CN 202410013312A CN 118005601 A CN118005601 A CN 118005601A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 75
- 230000002776 aggregation Effects 0.000 title claims abstract description 33
- 238000004220 aggregation Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 6
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 6
- 125000004986 diarylamino group Chemical group 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims description 14
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 13
- 239000005695 Ammonium acetate Substances 0.000 claims description 13
- 235000019257 ammonium acetate Nutrition 0.000 claims description 13
- 229940043376 ammonium acetate Drugs 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000007850 fluorescent dye Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000012984 biological imaging Methods 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 239000012216 imaging agent Substances 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 description 50
- 230000015572 biosynthetic process Effects 0.000 description 47
- 239000000047 product Substances 0.000 description 33
- -1 and if R 1 is O Chemical compound 0.000 description 31
- 239000000843 powder Substances 0.000 description 18
- MKYQPGPNVYRMHI-UHFFFAOYSA-N Triphenylethylene Chemical group C=1C=CC=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 MKYQPGPNVYRMHI-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 13
- 239000007787 solid Substances 0.000 description 11
- WAEMCQBNNIZRHC-UHFFFAOYSA-N 9H-xanthene-1,2-dione Chemical class C1=CC=C2OC(C=CC(C3=O)=O)=C3CC2=C1 WAEMCQBNNIZRHC-UHFFFAOYSA-N 0.000 description 9
- GJGAXDUUPRFUNG-UHFFFAOYSA-N acridine-1,2-dione Chemical class C1=CC=C2C=C(C(C(=O)C=C3)=O)C3=NC2=C1 GJGAXDUUPRFUNG-UHFFFAOYSA-N 0.000 description 9
- 150000003934 aromatic aldehydes Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- VUQVJIUBUPPCDB-UHFFFAOYSA-N (1-bromo-2,2-diphenylethenyl)benzene Chemical compound C=1C=CC=CC=1C(Br)=C(C=1C=CC=CC=1)C1=CC=CC=C1 VUQVJIUBUPPCDB-UHFFFAOYSA-N 0.000 description 4
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 description 4
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000005580 one pot reaction Methods 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- ISDBWOPVZKNQDW-UHFFFAOYSA-N 4-phenylbenzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC=CC=C1 ISDBWOPVZKNQDW-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 3
- 125000001475 halogen functional group Chemical group 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NPRFXRHWTRERQD-UHFFFAOYSA-N 1-methyl-1,2,3,4,5-pentakis-phenylsilole Chemical compound C=1C=CC=CC=1[Si]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 NPRFXRHWTRERQD-UHFFFAOYSA-N 0.000 description 2
- LBIYWHLOOHUEMH-UHFFFAOYSA-N 4-(2,2-diphenylethenyl)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 LBIYWHLOOHUEMH-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 2
- 238000007341 Heck reaction Methods 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- 238000007239 Wittig reaction Methods 0.000 description 2
- 125000005035 acylthio group Chemical group 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- VATYWCRQDJIRAI-UHFFFAOYSA-N p-aminobenzaldehyde Chemical compound NC1=CC=C(C=O)C=C1 VATYWCRQDJIRAI-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- UIGXGNUMMVHJKX-UHFFFAOYSA-N (4-formylphenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(C=O)C=C1 UIGXGNUMMVHJKX-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- UPJJNWCKFONBDW-UHFFFAOYSA-N 1-bromo-2-(1,2,2-triphenylethenyl)benzene Chemical group BrC1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 UPJJNWCKFONBDW-UHFFFAOYSA-N 0.000 description 1
- BBSNJTOHVHUCRF-OCEACIFDSA-N 1-bromo-4-[(e)-2-(4-bromophenyl)-1,2-diphenylethenyl]benzene Chemical group C1=CC(Br)=CC=C1C(\C=1C=CC=CC=1)=C(C=1C=CC(Br)=CC=1)/C1=CC=CC=C1 BBSNJTOHVHUCRF-OCEACIFDSA-N 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VDJSRXPVLSNTIP-UHFFFAOYSA-N C1(=CC=CC=C1)C(C(C1=CC=CC=C1)(C1=CC=CC=C1)Br)(C1=CC=CC=C1)Br Chemical compound C1(=CC=CC=C1)C(C(C1=CC=CC=C1)(C1=CC=CC=C1)Br)(C1=CC=CC=C1)Br VDJSRXPVLSNTIP-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000006323 alkenyl amino group Chemical group 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000006319 alkynyl amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000262 haloalkenyl group Chemical group 0.000 description 1
- 125000005291 haloalkenyloxy group Chemical group 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 125000000232 haloalkynyl group Chemical group 0.000 description 1
- 125000003106 haloaryl group Chemical group 0.000 description 1
- 125000004996 haloaryloxy group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000005844 heterocyclyloxy group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a compound with aggregation-induced emission performance and a preparation method thereof, and the compound has a structural general formula shown in the following formula (1): Wherein R 1 is O or NH, R 2 is a single bond, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; r 3 is H, substituted or unsubstituted phenyl, R 4、R5 is independently selected from H, substituted or unsubstituted C 1～8 aliphatic hydrocarbon, C 1～4 alkoxy, diaryl amino, carbazolyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, wherein the aliphatic hydrocarbon comprises at least one of alkyl, alkenyl or alkynyl. The structural compound of the scheme of the invention has weak luminous intensity in solution and emits strong fluorescence in an aggregation state, is an excellent aggregation-induced emission material, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a compound with aggregation-induced emission performance and a preparation method thereof.
Background
In recent years, research on organic light emitting materials has been significantly progressed, and important applications thereof have been made in the fields of display technology, illumination, sensors, biomedicine, and the like. However, the conventional organic light emitting materials have a problem of Aggregation-induced quenching (ACQ), that is, strong fluorescence is emitted in a solution state, but fluorescence is weakened or even quenched in a solid state, and the Aggregation-induced quenching limits practical application in solid state such as a thin film.
In 2001, tang Benzhong institute subject group found 1-methyl-1,2,3,4,5-pentaphenyl-silole (MPPS) series of compounds characterized in that the stronger the aggregation of molecules, the stronger the fluorescence emitted, (J.D.Luo,Z.L.Xie,J.W.Y.Lam,L.Cheng,H.Y.Chen,C.F.Qiu,H.S.Kwok,X.W.Zhan,Y.Q.Liu,D.B.Zhu,B.Z.Tang,Chem.Commun.2001,1740). the series of compounds hardly emitted fluorescence in solution, but emitted intense fluorescence in solid form. The concept of "Aggregation-Induced Emission" (AIE) is thus proposed and such materials are referred to as Aggregation-Induced Emission materials. The aggregation-induced emission concept provides a new idea for solving the problem of luminescent material ACQ. For decades, as the luminous efficiency of the material in a solid or aggregation state is far higher than that of a solution state, the material plays an important role in overcoming the aging problems of luminous materials and luminous devices and improving the luminous efficiency, and the material has obvious response to chemical environment and can be applied to chemical/biological sensors as a stimulus response material, the research of the material has become an emerging subject and has greatly progressed. Therefore, the development of new AIE materials is a current research hotspot. By regulating and controlling the aggregation state and intermolecular interaction of molecules, aggregation-induced luminescence effect can be realized, thereby improving the luminescence efficiency and stability. In addition, the AIE material can be functionally optimized through structural design and synthesis strategies so as to meet the requirements of different application fields. Therefore, the synthesis of new AIE materials, exploring practical applications in electronics, bioimaging, and sensors, etc., will drive technological advances and innovations in the relevant fields.
Based on this, it is important to develop a material having aggregation-induced emission properties.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a compound having aggregation-induced emission properties.
The invention also provides a preparation method of the compound.
The invention also provides application of the compound.
According to one aspect of the present invention, there is provided a compound having a general structural formula shown in the following formula (1):
Wherein R 1 is O or NH, R 2 is a single bond, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; r 3 is H, substituted or unsubstituted phenyl, R 4、R5 is independently selected from H, substituted or unsubstituted C 1～8 aliphatic hydrocarbon, C 1～4 alkoxy, diaryl amino, carbazolyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, wherein the aliphatic hydrocarbon comprises at least one of alkyl, alkenyl or alkynyl.
According to a preferred embodiment of the invention, there is at least the following effect: the compound of the scheme of the invention has weak luminous intensity in solution and emits strong fluorescence in an aggregation state, thus being an excellent aggregation-induced emission material.
In some preferred embodiments of the invention, R 2 is selected from one of the following structural formulas:
In some preferred embodiments of the invention, the R 4、R5 is independently selected from:
Wherein R 6 and R 7 are C 1～12 fatty alkyl groups.
In some preferred embodiments of the invention, the substitution is with phenyl, halo, alkyl, haloalkyl or cyano.
In some preferred embodiments of the invention, the compound is selected from one of the following structural formulas:
the invention also provides a preparation method of the compound, which comprises the following steps:
If R 1 in the compound shown in the formula (1) is O, carrying out Knoevenagel condensation reaction on the compound shown in the formula (2) and 1, 3-cyclohexanedione to obtain the compound;
If R 1 in the compound shown in the formula (1) is NH, carrying out Knoevenagel condensation reaction on the compound shown in the formula (2) and 1, 3-cyclohexanedione and ammonium acetate to obtain the compound;
Wherein the structural general formula of the compound shown in the formula (2) is as follows:
According to a preferred embodiment of the invention, there is at least the following effect: according to the scheme, 1,3 cyclohexanedione and a triphenylethylene or tetrastyrene group are subjected to a one-pot Knoevenagel condensation reaction to synthesize the AIE luminescent material xanthenedione derivative or acridine dione derivative with a novel structure. In the field of organic synthetic chemistry, knoevenagel condensation is an important reaction that can be used to build carbon-carbon double bonds and introduce functional groups. The structure of the triphenylethylene and the tetraphenylethylene not only has obvious aggregation-induced emission performance, but also has high thermal stability and luminous intensity, is used for preparing organic electroluminescent devices, other luminescent materials and the like, and has rich chemical structures and potential application values. 1, 3-cyclohexanedione is an important organic compound and is widely used in the fields of synthetic raw materials and pharmaceutical chemistry.
The scheme of the invention is that a compound with AIE performance is prepared by carrying out a simple one-pot Knoevenagel condensation reaction on a derivative of triphenylethylene or tetraphenyl ethylene, 1, 3-cyclohexanedione and ammonium acetate. By this method, high yield, high selectivity, low cost and simple operation can be achieved. The invention provides a reliable synthesis method which can be applied to the synthesis of various triphenylethylene or tetraphenylethylene derivatives and 1, 3-cyclohexanedione derivatives, has wide applicability and good potential economic benefit and expandability.
In some preferred embodiments of the present invention, the compound represented by the formula (2) may be synthesized into aromatic aldehydes containing triphenylethylene or tetraphenylethylene from benzophenone derivatives or triphenylethylene bromide by friedel-crafts alkylation, amine alkylation, halogenation, suzuki reaction, heck reaction, wittig reaction, etc. The synthesis is carried out by adopting a conventional organic synthesis method.
In some preferred embodiments of the present invention, the compound of formula (2) is selected from at least one of the following structures:
In some preferred embodiments of the invention, the Knoevenagel condensation reaction occurs under the catalysis of a catalytic system comprising MgCl 2 and acetic acid, and if R 1 is O, urea. The compounds of formula (1) comprise a xanthenedione derivative and an acridinedione derivative, and for xanthenedione derivatives, the preparation process comprises: synthesis of aromatic aldehyde group containing triphenylethylene or tetraphenylethylene; and (3) carrying out Knoevenagel condensation reaction on the 1, 3-cyclohexanedione and aromatic aldehyde groups. In the case of acridinedione derivatives, the main steps of the synthesis are as follows: synthesis of aromatic aldehyde group containing triphenylethylene or tetraphenylethylene; knoevenagel condensation of 1, 3-cyclohexanedione, aromatic aldehyde groups and ammonium acetate.
In some preferred embodiments of the present invention, the Knoevenagel condensation reaction is performed in a solvent system selected from at least one of absolute ethanol or absolute methanol.
In summary, the invention provides a high-efficiency synthesis method, which utilizes the Knoevenagel condensation reaction of the derivative of the tristyrene or the tetrapyrene and the 1, 3-cyclohexanedione to realize the synthesis of the target product. The method has the advantages of high yield, high selectivity, simplicity, convenience and the like, and can provide important application value for the fields of organic synthesis chemistry and pharmaceutical chemistry.
The invention also provides application of the compound in aggregation-induced emission.
In some embodiments of the invention, the aggregation-induced emission occurs in a poor solution; the poor solution is water.
The invention also provides application of the compound in preparing a fluorescence sensor.
The invention also provides application of the compound in preparing organic luminescent materials.
The invention also provides application of the compound in preparing a light-emitting device, a fluorescent probe, a fluorescent switch or a biological imaging agent.
The xanthenedione derivative and the acridine dione derivative containing the triphenylethylene or tetraphenylethylene structure provided by the invention have the advantages of capability of mechanochromism and recoverability in a powder state, obvious aggregation-induced emission characteristic in a poor solution, simple synthesis method, low raw material cost and easiness in large-scale commercial production. The serial product powder synthesized by the scheme of the invention has better piezochromic performance, is expected to have good potential application prospect in the fields of crack detection, anti-counterfeiting technology, electroluminescent devices, fluorescent probes, fluorescent switches, organism imaging and the like of woven fabrics, and expands the application field of AIE.
In the description of the present invention, the term "aliphatic hydrocarbon group" refers to alkyl groups, alkenyl groups, and alkynyl groups.
In the description of the present invention, the term "alkyl" refers to a saturated straight or branched chain aliphatic hydrocarbon group. Examples of C 1～8 alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl.
In the description of the present invention, the term "alkoxy" refers to a group of formula "-O-alkyl", and C 1～4 alkoxy includes methoxy, ethoxy, propoxy, butoxy.
In the description of the present invention, the term "aryl" represents an aromatic hydrocarbon group comprising one or more phenyl groups, preferably an aromatic hydrocarbon group of 6 to 10 carbon atoms, preferably phenyl.
In the description of the present invention, the term "substituted" means that the group may or may not be further substituted with one or more groups selected from: alkyl, alkenyl, alkynyl, aryl, halo (halo), haloalkyl, haloalkenyl, haloalkynyl, haloaryl, hydroxy, alkoxy, alkenyloxy, aryloxy, benzyloxy, haloalkyloxy, haloalkenyloxy, haloaryloxy, heteroaryl, nitro, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroaryl, nitroheterocyclyl, amino, alkylamino, dialkylamino, alkenylamino, alkynylamino, arylamino, diarylamino, phenylamino, diphenylamino, benzylamino, dibenzylamino, hydrazino, acyl, acylamino, diacylamino, acyloxy, heterocyclyl, heterocyclyloxy, heterocyclylamino, haloheterocyclyl, carboxyl esters, carboxyl, carboxyamides, mercapto, alkylthio, benzylthio, acyl thio (acylthio), and phosphorus-containing groups.
In the description of the present invention, the term "halogen" refers to fluorine, chlorine, bromine or iodine.
In the description of the present invention, the term "compound" is meant to include all stereoisomers, geometric isomers, tautomers and isotopes of the described structures. Unless otherwise indicated, a compound identified herein by name or structure as one particular tautomeric form is intended to include other tautomeric forms. It is to be understood that certain compounds provided herein may contain one or more asymmetric centers and thus may be prepared and isolated as mixtures of isomers, such as racemic mixtures, or in enantiomerically pure form.
In the description of the present invention, the term "tautomer" refers to a compound whose structure is significantly different in the arrangement of atoms but is present in a simple and rapid equilibrium, and it is understood that the compounds provided herein can be depicted as different tautomers, and that when the compounds have tautomeric forms, all tautomeric forms are within the scope of the present invention, and that the naming of the compounds does not exclude any tautomers.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a graph showing changes in fluorescence intensity of a tetrahydrofuran solution of the compound (9- (4- (1, 2-triphenylvinyl) phenyl) -3,4,5,6,7, 9-hexahydro-1H-xanthene-1, 8 (2H) -dione) obtained in example 1 according to the present invention, after adding various volumes of water.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention. The experimental methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are those commercially available. Unless otherwise indicated, the same parameter is the same in each embodiment. The following examples are illustrative only and are not to be construed as limiting the invention.
In the description of the present invention, the descriptions of the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
In the description of the invention, room temperature is 25.+ -. 5 ℃ and in particular 25 ℃ in the examples.
The invention provides a xanthenedione derivative or an acridine dione derivative containing a triphenylethylene or tetraphenylethylene structure, the structure of which is shown as a general formula (1):
Wherein R 1 is O, NH; r 2 is a single bond, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; r 3 is H, substituted or unsubstituted phenyl, R 4、R5 is independently selected from H, C 1～8 alkyl, C 1～4 alkoxy, diarylamino, carbazolyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and the aliphatic hydrocarbon group comprises at least one of alkyl, alkenyl or alkynyl.
The preparation process is as follows:
The first step: synthesis of aromatic aldehydes containing triphenylethylene or tetraphenylethylene
The method is characterized in that benzophenone derivatives or triphenylethylene bromine are used as raw materials, and synthesis is carried out by adopting a conventional organic synthesis method, wherein the synthesis comprises Friedel-crafts alkylation, amine alkylation, halogenation, suzuki reaction, heck reaction, wittig reaction and the like to synthesize aromatic aldehyde containing triphenylethylene or tetraphenylethylene, and the structure of the aromatic aldehyde is shown as a general formula (2):
The preferred structure of the aromatic aldehyde is as follows:
and a second step of:
The synthesized intermediate and 1, 3-cyclohexanedione take absolute ethyl alcohol as a solvent, and are subjected to ring closure under the catalysis of anhydrous MgCl 2, acetic acid and urea to generate a xanthenedione derivative, wherein the reaction formula is as follows:
The synthesized intermediate, 1, 3-cyclohexanedione and ammonium acetate take absolute ethyl alcohol as a solvent, and are subjected to ring closure under the catalysis of anhydrous MgCl 2 and acetic acid to generate the acridine dione derivative, wherein the reaction formula is as follows:
The invention designs a xanthenedione derivative, an acridine dione derivative and a preparation method thereof, and synthesis of the xanthenedione derivative: aromatic aldehyde group compound containing a triphenylethylene or tetraphenylethylene structure, 1, 3-cyclohexanedione, urea, anhydrous MgCl 2 and acetic acid are synthesized by a one-pot method; synthesis of acridinedione derivatives: aromatic aldehyde group compound containing a triphenylethylene or tetraphenylethylene structure, 1, 3-cyclohexanedione, ammonium acetate, anhydrous MgCl 2 and acetic acid are synthesized by a one-pot method. The xanthenedione derivative and the acridine dione derivative containing the triphenylethylene or tetraphenylethylene structure provided by the invention have obvious aggregation-induced emission characteristics in poor solution, and the synthesis method is simple, low in raw material cost and easy for large-scale commercial production. The serial product powder synthesized by the scheme of the invention has better piezochromic performance, is expected to have good potential application prospect in the fields of crack detection, anti-counterfeiting technology, electroluminescent devices, fluorescent probes, fluorescent switches, organism imaging and the like of woven fabrics, and expands the application field of AIE.
Example 1
The compound with aggregation-induced emission properties is prepared in the embodiment, and the specific preparation process is as follows:
(1) Synthesis of intermediate tetraphenylvinyl aldehyde:
Triphenylbromoethylene (3.35 g,10 mmol) and 4-formylphenylboronic acid (1.5 g,10 mmol) were added to a three-necked flask under an atmosphere of N 2, then 50mL of Tetrahydrofuran (THF), 18mL of 2mol/L aqueous potassium carbonate, tetrabutylammonium bromide (TBAB) (0.32 g,1.0 mmol), stirred at room temperature and passed through N 2 for half an hour, pd (PPh 3)4(0.010g,8.7×10- 3 mmol) was added and the mixture was warmed to 90℃for 24 hours. Then pouring the reaction solution into water, extracting with ethyl acetate for three times, drying the organic layer with anhydrous sodium sulfate, removing the solvent by rotary evaporation under reduced pressure, purifying by using a silica gel column chromatography method, and eluting with a mixed solvent of dichloromethane and n-hexane in a volume ratio of 1:2. 3.25g of product was obtained in 97% yield.
(2) Synthesis of target product
① Synthesis of 9- (4- (1, 2-triphenylvinyl) phenyl) -3,4,5,6,7, 9-hexahydro-1H-xanthene-1, 8 (2H) -dione:
TPEA (0.361 g,1 mmol) and 30mL of absolute ethanol were added to a three-necked flask, and the mixture was heated to 75℃with stirring. After TPEA was sufficiently dissolved, anhydrous magnesium chloride (0.019 g,0.2 mmol) and catalyst acetic acid (9 mL, 30% ethanol) were added, and stirring was continued for 10min with heating, and urea (0.06 g,1 mmol) and 1,3 cyclohexanedione (0.196 g,2 mmol) were added and reacted for 24h. Suction filtration and repeated washing of the filter residue with ethanol for 3 times gave a white powder (0.44 g, 80%).
② Synthesis of 9- (4- (1, 2-triphenylvinyl) phenyl) -3,4,6,7,9, 10-hexahydroacridine-1, 8 (2H, 5H) -dione:
TPEA (0.361 g,1 mmol) was added to 30mL of absolute ethanol and heated with stirring. After TPEA was sufficiently dissolved, anhydrous magnesium chloride (0.019 g,0.2 mmol) and catalyst acetic acid (9 mL, 30% of ethanol) were added, stirring was continued at 90℃for 10min, and ammonium acetate (0.078 g,1 mmol) and 1,3 cyclohexanedione (0.196 g,2 mmol) were added to a three-necked flask and reacted for 24 h. Suction filtration and repeated washing of the filter residue with ethanol for 3 times gave a white powder (0.43 g, 79%).
Example 2
The compound with aggregation-induced emission properties is prepared in the embodiment, and the specific preparation process is as follows:
(1) Synthesis of intermediate 4' - (1, 2-triphenylethylene) biphenyl-4-carbaldehyde:
Tetraphenylethylene bromide (4.11 g,10.0 mmol) and 4-formylphenylboric acid (1.49 g,10.0 mmol) were added to a three-necked flask, 60mL of tetrahydrofuran, 15mL of an aqueous solution of 2MK 2CO3, tetrabutylammonium bromide (TBAB) (0.64 g,2.0 mmol) were added, argon was introduced for 40min, a catalyst amount Pd (PPh 3)4) was added, the reaction was completed by heating to 85℃in an oil bath, extraction was performed with water, the organic phase was dried with anhydrous sodium sulfate, and then dried under reduced pressure in a rotary evaporator to obtain a crude product.
(2) Synthesis of target product
① Synthesis of 9- (4,2,2-triphenylvinyl) -1, 1-biphenyl-4-yl) -3,4,5,6,7, 9-hexahydro-1H-xanth-1, 8 (2H) -dione:
The synthesis of 9- (4,2,2-triphenylvinyl) -1, 1-biphenyl-4-yl) -3,4,5,6,7, 9-hexahydro-1H-xanthene-1, 8 (2H) -dione, the target product, designated by reference numeral ① in example 1 (2), was obtained by reacting 4' - (1, 2-triphenylethylene) biphenyl-4-carbaldehyde with 1,3 cyclohexanedione. The product was 0.45g of grey powder with 73% yield.
② Synthesis of 9- (4 '- (1, 2-triphenylvinyl) - [1,1' -biphenyl ] -4-yl) -3,4,6,7,9, 10-hexahydroacridine-1, 8 (2H, 5H) -dione:
The synthesis of the target product 9- (4 ' - (1, 2-triphenylvinyl) - [1,1' -biphenyl ] -4-yl) -3,4,6,7,9, 10-hexahydroacridine-1, 8 (2H, 5H) -dione was obtained by reacting 4' - (1, 2-triphenylethylene) biphenyl-4-carbaldehyde, 1,3 cyclohexanedione, and ammonium acetate, see SEQ ID NO. ② in example 1 (2). The product was 0.44g of grey powder with a yield of 71%.
Example 3
The compound with aggregation-induced emission properties is prepared in the embodiment, and the specific preparation process is as follows:
(1) Synthesis of intermediate 4- (2, 2-biphenylvinyl) benzaldehyde:
Triphenylethylene bromide (3.35 g,10.0 mmol) was dissolved in 20mL tetrahydrofuran, cooled to-78deg.C, and a 2.5M solution of n-butyllithium (4.0 mL,10.0 mmol) was slowly added dropwise. After completion of the dropwise addition for 2 hours, N-dimethylformamide (1.46 g,20.0 mL) was added, and the mixture was allowed to warm to room temperature and reacted for 24 hours. After the reaction is finished, extraction is carried out by water, and the organic phase is dried by anhydrous sodium sulfate and then dried by decompression in a rotary evaporator, thus obtaining a crude product. Purifying by silica gel column chromatography, wherein the eluent is mixed solvent of n-hexane and dichloromethane with a volume ratio of 3:1. The pure product was 3.3g of a white solid with a yield of 81%.
(2) Synthesis of target product
① Synthesis of 9- (4- (2, 2-diphenylvinyl) phenyl-3, 4,5,6,7, 9-hexahydro-1H-xanthene-1, 8 (2H) -dione:
The synthesis of 9- (4- (2, 2-diphenylvinyl) phenyl-3, 4,5,6,7, 9-hexahydro-1H-xanthene-1, 8 (2H) -dione, which was obtained by reacting 4- (2, 2-diphenylvinyl) benzaldehyde with 1, 3-cyclohexanedione, was conducted according to the procedure of example 1 (2) and gave a pure product as a white powder (0.38 g, 80% yield).
② Synthesis of 9- (4- (2, 2-diphenylvinyl) phenyl) -3,4,6,7,9, 10-hexahydroacridine-1, 8 (2H, 5H) -dione:
the synthesis of the target product 9- (4- (2, 2-diphenylvinyl) phenyl) -3,4,6,7,9, 10-hexahydroacridine-1, 8 (2H, 5H) -dione was obtained by reacting 4- (2, 2-diphenylvinyl) benzaldehyde, 1,3 cyclohexanedione and ammonium acetate according to the procedure given in example 1 (2) No. ②. The pure product was 0.36g of white powder with a yield of 78%.
Example 4
The compound with aggregation-induced emission properties is prepared in the embodiment, and the specific preparation process is as follows:
(1) Intermediate 4'- (2, 2-stilbene) - [1,1' -biphenyl ] -4-carbaldehyde was synthesized according to the procedure of example 2 (1). Is prepared from bromotriphenylethylene and p-aldehyde phenylboronic acid through reaction. The product was 2.8g of a white powder with a yield of 78%.
(2) Synthesis of target product
① Synthesis of 9- (4, 2-diphenylvinyl) - [1,1' -biphenyl ] -4-yl) -3,4,5,6,7, 9-hexahydro-1H-xanthene-1, 8 (2H) -dione:
The synthesis of the target product 9- (4, 2-diphenylvinyl) - [1,1' -biphenyl ] -4-yl) -3,4,5,6,7, 9-hexahydro-1H-xanthene-1, 8 (2H) -dione was obtained by reacting 4' - (2, 2-stilbene) - [1,1' -biphenyl ] -4-carbaldehyde with 1,3 cyclohexanedione, according to the method of example 1 (2) No. ①. The pure product was 0.42g of white powder with a yield of 76%.
② Synthesis of 9- (4 '- (2, 2-diphenylvinyl) - [1,1' -biphenyl ] -4-yl) -3,4,6,7,9, 10-hexahydroacridine-1, 8 (2H, 5H) -dione:
The synthesis of the target product 9- (4 '- (2, 2-diphenylvinyl) - [1,1' -biphenyl ] -4-yl) -3,4,6,7,9, 10-hexahydroacridine-1, 8 (2H, 5H) -dione was obtained by reacting 4'- (2, 2-diphenylvinyl) - [1,1' -biphenyl ] -4-carbaldehyde, 1,3 cyclohexanedione, and ammonium acetate, see (2) No. ② in example 1. The pure product was 0.4g of white powder with a yield of 73%.
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Example 5
The compound with aggregation-induced emission properties is prepared in the embodiment, and the specific preparation process is as follows:
(1) Synthesis of intermediate 5- (4- (1, 2-triphenylvinyl) phenyl) thiophene-2-carbaldehyde by the method of reference example 2 (1), 5-aldehyde-2-thiopheneboronic acid was used instead of 4-aldehyde phenylboronic acid, and bromotetraphenyl ethylene was synthesized as a pale yellow powder 3.75g with a yield of 85%.
(2) Synthesizing a target product:
① Synthesis of 9- (5- (4- (1, 2-triphenylvinyl) phenyl) thiophen-2-yl) -3,4,5,6,7, 9-hexahydro-1H-xanth-1, 8 (2H) -dione:
Synthesis of the target product 9- (5- (4- (1, 2-triphenylvinyl) phenyl) thiophen-2-yl) -3,4,5,6,7, 9-hexahydro-1H-xanthene-1, 8 (2H) -dione 0.47g was obtained by reacting 5- (4- (1, 2-triphenylvinyl) phenyl) thiophen-2-carbaldehyde with 1,3 cyclohexanedione according to the procedure of (2) in example 1 with reference numeral ①. The yield was 75%.
② Synthesis of 9- (5- (4- (1, 2-triphenylvinyl) phenyl) thiophen-2-yl) -3,4,6,7,9, 10-hexahydroacridine-1, 8 (2H, 5H) -dione:
Synthesis of the target product 9- (5- (4- (1, 2-triphenylvinyl) phenyl) thiophen-2-yl) -3,4,6,7,9, 10-hexahydroacridine-1, 8 (2H, 5H) -dione 0.44g was obtained by reacting 5- (4- (1, 2-triphenylvinyl) phenyl) thiophen-2-carbaldehyde, 1, 3-cyclohexanedione and ammonium acetate with reference to the sequence number ② in example 1 (2).
The yield was 71%.
Example 6
The compound with aggregation-induced emission properties is prepared in this example, and has the structure:
The preparation process comprises the following steps:
(1) Synthesis of intermediate (E) -4' - (2- ([ 1,1' -biphenyl ] -4-yl) -1, 2-diphenylvinyl) - [1,1' -biphenyl ] -4-carbaldehyde:
(E) -4- (2- (4-bromophenyl) -1, 2-diphenylvinyl) -1,1 '-biphenyl was reacted with 4-formylphenylboronic acid to give the product (E) -4' - (2- ([ 1,1 '-biphenyl ] -4-yl) -1, 2-diphenylvinyl) - [1,1' -biphenyl ] -4-carbaldehyde.
(2) Synthesis of the target product (E) -9- (4 ' - (2- ([ 1,1' -biphenyl ] -4-yl) -1, 2-diphenylvinyl) - [1,1' -biphenyl ] -4-yl) -3,4,6,7,9, 10-hexahydroacridine-1, 8 (2H, 5H) -dione:
(E) -4'- (2- ([ 1,1' -biphenyl ] -4-yl) -1, 2-diphenylvinyl) - [1,1 '-biphenyl ] -4-carbaldehyde was reacted with 1, 3-cyclohexanedione, ammonium acetate to give the product (E) -9- (4' - (2- ([ 1,1 '-biphenyl ] -4-yl) -1, 2-diphenylvinyl) - [1,1' -biphenyl ] -4-yl) -3,4,6,7,9, 10-hexahydroacridine-1, 8 (2H, 5H) -dione.
The target compound is prepared by nuclear magnetic characterization.
Example 7
The compound with aggregation-induced emission properties is prepared in this example, and has the structure:
The preparation process comprises the following steps:
(1) Synthesis of intermediate (E) -9- (4- (2- (4-bromophenyl) -1, 2-diphenylvinyl) phenyl) -9H-carbazole:
(E) -1, 2-bis (4-bromophenyl) -1, 2-diphenylethylene and 9H-carbazole are reacted with palladium diacetate and tri-tert-butylphosphine as catalysts to form (E) -9- (4- (2- (4-bromophenyl) -1, 2-diphenylvinyl) phenyl) -9H-carbazole.
(2) Synthesis of intermediate (E) -4'- (2- (4- (9H-carbazol-9-yl) phenyl) -1, 2-diphenylvinyl) - [1,1' -biphenyl ] -4-carbaldehyde:
(E) -9- (4- (2- (4-bromophenyl) -1, 2-diphenylvinyl) phenyl) -9H-carbazole is reacted with 4 formylphenylboronic acid to give (E) -4'- (2- (4- (9H-carbazol-9-yl) phenyl) -1, 2-diphenylvinyl) - [1,1' -biphenyl ] -4-carbaldehyde.
(3) Synthesis of the target product (E) -9- (4 '- (2- (4- (9H-carbazol-9-yl) phenyl) -1, 2-diphenylvinyl) - [1,1' -biphenyl ] -4-yl) -3,4,6,7,9, 10-hexahydroacridine-1, 8 (2H, 5H) -dione:
(E) -4'- (2- (4- (9H-carbazol-9-yl) phenyl) -1, 2-diphenylvinyl) - [1,1' -biphenyl ] -4-carbaldehyde and 1,3 cyclohexanedione were reacted with acetic acid over catalyst MgCl2 to form (E) -9- (4 '- (2- (4- (9H-carbazol-9-yl) phenyl) -1, 2-diphenylvinyl) - [1,1' -biphenyl ] -4-yl) -3,4,6,7,9, 10-hexahydroacridine-1, 8 (2H, 5H) -dione.
The target compound is prepared by nuclear magnetic characterization.
Example 8
The compound with aggregation-induced emission properties is prepared in this example, and has the structure:
The preparation process comprises the following steps:
(1) Synthesis of intermediate 4'- (1, 2-triphenylvinyl) - [1,1' -biphenyl ] -4-carbaldehyde:
(2- (4-bromophenyl) ethylene-1, 2-tri-yl) triphenyl is reacted with 4-formylphenylboronic acid to give the product 4'- (1, 2-triphenylvinyl) - [1,1' -biphenyl ] -4-carbaldehyde.
(2) Synthesis of intermediate (E) -4- (2- (4 '- (1, 2-triphenylvinyl) - [1,1' -biphenyl ] -4-yl) vinyl) benzaldehyde:
4'- (1, 2-triphenylvinyl) - [1,1' -biphenyl ] -4-carbaldehyde is reacted with 4-aminobenzaldehyde to obtain the product (E) -4- (2- (4 '- (1, 2-triphenylvinyl) - [1,1' -biphenyl ] -4-yl) vinyl) benzaldehyde.
(3) Synthesis of the target product (E) -9- (4- (2- (4 '- (1, 2-triphenylvinyl) - [1,1' -biphenyl ] -4-yl) vinyl) phenyl) -3,4,6,7,9, 10-hexahydroacridine-1, 8 (2H, 5H) -dione:
(E) -4- (2- (4 '- (1, 2-triphenylvinyl) - [1,1' -biphenyl ] -4-yl) vinyl) benzaldehyde, and 1, 3-cyclohexanedione, ammonium acetate to give the product (E) -9- (4- (2- (4 '- (1, 2-triphenylvinyl) - [1,1' -biphenyl ] -4-yl) vinyl) phenyl) -3,4,6,7,9, 10-hexahydroacridine-1, 8 (2 h,5 h) -dione.
The target compound is prepared by nuclear magnetic characterization.
Test examples
The structure of the compound prepared in the example and the maximum fluorescence emission wavelength, fluorescence quantum efficiency and aggregation-induced emission effect of the solid powder were tested in this test example. Wherein:
by nuclear magnetism and mass spectrometry analysis, the products with target structures are obtained in the embodiments of the scheme.
The maximum fluorescence emission wavelength was measured by using an RF-5301pc fluorescence spectrophotometer of Shimadzu corporation; the fluorescence quantum efficiency of the solid powder is measured by using a test solid fluorescence quantum efficiency test system consisting of a Maya 2000Pro optical fiber spectrometer of ocean optics, a C-701 integrating sphere of blue phenanthrene company of America and an ocean optics LLS-LED light source according to the method of Adv. Mater.1997,9, 230-232.
The measurement results are shown in table 1 below.
TABLE 1 maximum fluorescence emission wavelength and fluorescence quantum efficiency of solid powders of the compounds of examples 1 to 5
Note that: Represents the maximum fluorescence emission wavelength of the sample solid powder, and phi F represents the fluorescence quantum efficiency of the solid powder. /(I)
Only the results of the detection of a part of the compounds are shown in the table, and the results of the compounds prepared in other examples are equivalent, and are not shown one by one in order to avoid redundancy.
To investigate the AIE properties of the compounds of the present invention, the solution of the compound in tetrahydrofuran was added with water as a poor solvent, and the change in fluorescence intensity of the solution was observed with the difference in the added water content. As can be seen from FIG. 1, when the water content is lower than 90%, the fluorescence intensity and change of the solution are weak, but when the water content reaches 90%, the fluorescence intensity of the solution is suddenly increased, which is 20 times that of the pure tetrahydrofuran solution. I.e. the data indicate that the compounds of the present scheme have good AIE properties.
From the results, the compounds of the scheme have good aggregation-induced emission effect, so that the compounds have good application prospects in the fields of preparation of organic luminescent materials, fluorescent sensors, luminescent devices, fluorescent probes, fluorescent switches or biological imaging agents and the like.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. A compound, characterized in that: has a structural general formula shown in the following formula (1):
Wherein R 1 is O or NH, R 2 is a single bond, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; r 3 is H, substituted or unsubstituted phenyl, R 4、R5 is independently selected from H, substituted or unsubstituted C 1～8 aliphatic hydrocarbon, C 1～4 alkoxy, diaryl amino, carbazolyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, wherein the aliphatic hydrocarbon comprises at least one of alkyl, alkenyl or alkynyl.
2. A compound according to claim 1, characterized in that: r 2 is selected from one of the following structural formulas:
and/or, the R 4、R5 is independently selected from:
Wherein R 6 and R 7 are C 1～12 fatty alkyl groups.
3. A compound according to claim 1, characterized in that: the substitution is with phenyl, halogen, alkyl, haloalkyl or cyano; preferably, the compound is selected from one of the following structural formulas:
4. a process for the preparation of a compound according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
If R 1 in the compound shown in the formula (1) is O, carrying out Knoevenagel condensation reaction on the compound shown in the formula (2) and 1, 3-cyclohexanedione to obtain the compound;
If R 1 in the compound shown in the formula (1) is NH, carrying out Knoevenagel condensation reaction on the compound shown in the formula (2) and 1, 3-cyclohexanedione and ammonium acetate to obtain the compound;
Wherein the structural general formula of the compound shown in the formula (2) is as follows:
5. The method of manufacturing according to claim 4, wherein: the compound shown in the formula (2) is at least one of the following structures:
6. The method of manufacturing according to claim 4, wherein: the Knoevenagel condensation reaction occurs under the catalysis of a catalytic system, wherein the catalytic system comprises MgCl 2 and acetic acid, and if R 1 is O, the catalytic system further comprises urea; the Knoevenagel condensation reaction is carried out in a solvent system, wherein the solvent system is at least one of absolute ethyl alcohol or absolute methyl alcohol.
7. Use of a compound according to any one of claims 1 to 3 for aggregation-induced emission.
8. Use of a compound according to any one of claims 1 to 3 for the preparation of a fluorescence sensor.
9. Use of a compound according to any one of claims 1 to 3 for the preparation of an organic light-emitting material.
10. Use of a compound according to any one of claims 1 to 3 for the preparation of a light emitting device, a fluorescent probe, a fluorescent switch or a biological imaging agent.
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