CN115504926B - Novel low Wen Chaochang afterglow molecular material and preparation method thereof - Google Patents
Novel low Wen Chaochang afterglow molecular material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 17
- 239000004305 biphenyl Substances 0.000 claims abstract description 17
- 150000001492 aromatic hydrocarbon derivatives Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 78
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 12
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 10
- 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 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 7
- 239000012312 sodium hydride Substances 0.000 claims description 7
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 7
- 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 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- OYFFSPILVQLRQA-UHFFFAOYSA-N 3,6-ditert-butyl-9h-carbazole Chemical compound C1=C(C(C)(C)C)C=C2C3=CC(C(C)(C)C)=CC=C3NC2=C1 OYFFSPILVQLRQA-UHFFFAOYSA-N 0.000 claims description 5
- 229940124530 sulfonamide Drugs 0.000 claims description 5
- 150000003456 sulfonamides Chemical class 0.000 claims description 5
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 230000002862 amidating effect Effects 0.000 claims description 2
- 238000007112 amidation reaction Methods 0.000 claims description 2
- 238000012984 biological imaging Methods 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 2
- 239000000523 sample Substances 0.000 claims description 2
- 238000003745 diagnosis Methods 0.000 claims 1
- 201000010099 disease Diseases 0.000 claims 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 230000005855 radiation Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000005283 ground state Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000011368 organic material Substances 0.000 abstract description 3
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 120
- 238000004896 high resolution mass spectrometry Methods 0.000 description 67
- 238000004949 mass spectrometry Methods 0.000 description 65
- 229920000642 polymer Polymers 0.000 description 65
- 239000007787 solid Substances 0.000 description 63
- 229940126062 Compound A Drugs 0.000 description 27
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- -1 2-substituted benzene ring Chemical group 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 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 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001555 benzenes Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- HJCUTNIGJHJGCF-UHFFFAOYSA-N 9,10-dihydroacridine Chemical compound C1=CC=C2CC3=CC=CC=C3NC2=C1 HJCUTNIGJHJGCF-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 230000001443 photoexcitation Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000001906 matrix-assisted laser desorption--ionisation mass spectrometry Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000005581 pyrene group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- 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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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Abstract
The invention discloses a low-temperature ultra-long afterglow molecular material and a preparation method thereof. The structural formula of the low-temperature ultra-long afterglow molecular material is shown as a formula TM. The low Wen Chaochang afterglow molecular material provided by the invention is a series of pure organic materials, wherein each organic material has extremely fast intersystem crossing rate (from a first singlet state to a triplet state) and extremely slow phosphorescent radiation rate (from the first triplet state to a ground state), and macroscopically shows continuous luminescence at a low temperature for 18-40 seconds. The method for preparing the aromatic hydrocarbon derivative based on the biphenyl structure has the advantages of low-cost and easily-obtained raw materials, simple and efficient synthesis steps, high reaction yield and easy separation. The aromatic hydrocarbon derivative based on the biphenyl structure provided by the invention has good solubility, thermal stability and electrochemical stability, and has wide application prospects in the field of continuous luminescent materials.
Description
Technical Field
The invention relates to a novel low Wen Chaochang afterglow molecular material and a preparation method thereof, belonging to the field of organic luminescent material chemistry.
Background
Ultra-long afterglow materials in very low temperature environments are a class of materials with special phenomena and potential applications. Such materials, in very low temperature environments, can emit very intense and very long-lived phosphorescence upon photoexcitation. After the excitation light source is turned off, the light continues to emit for 20-60 seconds. From photophysical process analysis, such materials exhibit extremely fast intersystem crossing rates (from the first singlet state to the triplet state) and extremely slow phosphorescent radiation transition rates (from the first triplet state to the ground state) at extremely low temperatures. Thus, upon photoexcitation, such materials rapidly accumulate a large number of triplet excitons, and then release the triplet energy very slowly back to the ground state. The faster the intersystem crossing rate of such materials, the slower the phosphorescent radiation transition rate, the longer afterglow is exhibited at low temperatures. Based on this special property, such materials have many potential applications in very low temperature environments, such as encryption anti-counterfeiting, biological imaging, optical temperature probes.
Disclosure of Invention
The invention aims to provide an ultra-long low-temperature afterglow material based on a biphenyl structure, wherein each molecule of the material shows thermal activation delayed fluorescence property and ultra-long low-temperature long afterglow phenomenon, is a special functional material further used in an ultra-low temperature environment, and can be applied to the fields of extreme environments and the like.
The structural formula of the aromatic hydrocarbon derivative based on the biphenyl structure is shown as a formula TM;
In the formula TM, the radical donor is an electron-rich donor radical selected from carbazole and 3, 6-di-tert-butylcarbazole;
the group X is selected from benzene ring, substituted benzene ring, naphthalene ring, perylene ring, pyrene ring, carbazole, 3, 6-di-tert-butylcarbazole, 9, 10-dihydroacridine, phenoxazine and phenothiazine.
Specifically, the substituted benzene ring is any one of a 2-substituted benzene ring, a 3-substituted benzene ring, a 4-substituted benzene ring, a3, 5-disubstituted benzene ring and a2, 4, 6-trisubstituted benzene ring, wherein the substituent is any one of methyl, methoxy, amino, cyano, aldehyde, ester and phenylcarbonyl.
The aromatic hydrocarbon derivative with the biphenyl structure provided by the invention is preferably any one of the following structures:
the invention also provides a preparation method of the aromatic hydrocarbon derivative with the biphenyl structure, which comprises the following steps:
1) Amidating the compound shown in the formula A 1 with sulfonamide and dehydrating to obtain a compound shown in the formula B 1;
The method can convert carboxylic acid into cyano with high efficiency under the condition that bromine atoms and fluorine atoms on the benzene ring are not destroyed;
2) The compound shown in the formula B 1 is reacted with sodium hydride firstly and then reacted with a compound corresponding to an electron donating group donor to obtain a compound shown in the formula C 1;
The feeding ratio is well controlled, and the electron donating group donor can preferentially react with the strong electron-withdrawing fluorine atoms on the benzene ring with high efficiency, so that the electron donating group donor is difficult to react with the bromine atoms on the benzene ring.
The electron donating group donor is an electron rich donor group selected from carbazole and 3, 6-di-tert-butylcarbazole;
3) Carrying out Suzuki coupling reaction or Buchwald-Hartwig coupling reaction on a compound shown in a formula C 1 and a compound corresponding to a group X under the catalysis of a palladium catalyst and alkali to obtain an aromatic hydrocarbon derivative with a biphenyl structure shown in a formula TM;
the definition of the group X is the same as the formula TM.
In the above preparation method, in step 1), the amidation and dehydration reaction is performed in sulfolane;
the molar ratio of the compound represented by formula a 1 to the sulfonamide is 1: 2-1: 4, a step of;
the compound represented by formula A 1 can be produced according to the method described in the prior document (Chin.J.Org.Chem.2013, 33,2349.DIO:10.6023/cjoc 201306029);
The electrophilic substitution reaction is carried out as follows: firstly, reacting for 3 to 4 hours at 160 ℃, transferring to room temperature and cooling for 0.5 to 1 hour;
The reaction does not require inert gas shielding.
In the preparation method, in the step 2), the nucleophilic substitution reaction is to react a compound shown in a formula B 1 with sodium hydride in dry N, N-dimethylformamide for 0.5 to 1 hour at room temperature, then adding an electron donating group donor, and continuing to react for 10 to 12 hours at the temperature of 60 to 80 ℃;
the molar ratio of the formula B 1 to the compound corresponding to the sodium hydride to the electron donating group donor is 1:1.1 to 1.2:2;
The reaction requires an inert gas blanket.
In the preparation method, in the step 3), the conditions of the Suzuki coupling reaction are as follows:
In the presence of tetrakis (triphenylphosphine) palladium and potassium carbonate;
The molar ratio of the compound shown in the formula C 1 or the compound shown in the formula C 2, the compound corresponding to the group X, the tetra (triphenylphosphine) palladium and the potassium carbonate is 1:1 to 1.05:0.05 to 0.1:5 to 8;
The solvent is a mixed solution of toluene and water, and the volume ratio is 1:0.3 to 0.5;
The reaction temperature is 105-110 ℃;
the reaction time is 20-24 hours;
An inert gas blanket is required.
In the preparation method, in the step 3), the conditions of the Buchwald-Hartwig coupling reaction are as follows:
In the presence of tris (dibenzylideneacetone) dipalladium and sodium tert-butoxide;
The molar ratio of the compound shown in the formula C 1 or the compound shown in the formula C 2, the compound corresponding to the group X, the tris (dibenzylideneacetone) dipalladium to the sodium tert-butoxide is 1:1 to 1.05:0.05 to 0.1:5 to 8;
The solvent is dry toluene;
The reaction temperature is 105-110 ℃;
the reaction time is 20-24 hours;
An inert gas blanket is required.
The compound corresponding to the substituent X is specifically a compound shown in the following formula a 1-a33:
The aromatic hydrocarbon derivative based on the biphenyl structure shown in the formula TM is a series of pure organic materials, wherein each organic matter has extremely fast intersystem crossing rate (from a first singlet state to a triplet state) and extremely slow phosphorescence radiation rate (from the first triplet state to a ground state), and macroscopically shows continuous luminescence at a low temperature for 18-40 seconds.
The method for preparing the aromatic hydrocarbon derivative based on the biphenyl structure has the advantages of low-cost and easily-obtained raw materials, simple and efficient synthesis steps, high reaction yield and easy separation.
The aromatic hydrocarbon derivative based on the biphenyl structure provided by the invention has good solubility, thermal stability and electrochemical stability, and has wide application prospects in the field of continuous luminescent materials.
Drawings
FIG. 1 is a graph demonstrating the phosphorescent lifetime decay curve (a) and long afterglow pattern (b) of the low-temperature long afterglow small molecules of the invention in liquid nitrogen.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are all available from commercial sources or reported documents unless otherwise specified.
The reaction route of the biphenyl-based aromatic hydrocarbon derivative shown in the synthetic formula TM is shown as follows:
Intermediates C 1 and C 2 in the present invention are key intermediates of the present invention and in each case need to be passed through both intermediate compounds.
The specific synthetic steps for intermediates C 1 and C 2 are as follows:
The specific step I in the invention is as follows: to a 100mL two-necked round bottom flask at room temperature was added compound A 1 (4.36 g,10mmol,1.0 equiv), 30mL thionyl chloride solvent, and a catalytic amount of 4-dimethylaminopyridine (48.9 mg,0.4mmol,0.04 equiv), and the mixture was then added to reflux and stirred for 5 hours. After the reaction was completed, excess thionyl chloride was distilled off under reduced pressure, then sulfonamide (2.88 g,30mmol,3 equiv) and sulfolane (10 mL) were added to the round bottom flask and the temperature was raised to 160℃and stirring was continued for 3 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and 80 ml of 1 mol/L aqueous sodium hydroxide solution was added thereto and stirred for several minutes. The precipitate was allowed to stand and filtered, and the residue was purified by column chromatography (petroleum ether: dichloromethane=5:4 as mobile phase) to give 1.27g of white solid powder B 1 in 32% yield.
The specific step II in the invention is as follows: to a 100mL two-necked round bottom flask was added carbazole (1.67 g,10mmol,2.5 equiv), sodium hydride (440 mg,11mmol,2.75equiv,60% dispersed in mineral oil) and N, N-dimethylformamide (40 mL) and stirred at room temperature under nitrogen for 2 hours. The compound of formula B 1 (1.59 g,4mmol,1.0 equiv) was added slowly and the mixture was then heated to 70℃for 12 hours with stirring. After the completion of the reaction, the reaction mixture was poured into 40mL of water, allowed to stand for precipitation and filtration, and the residue was purified by column chromatography (petroleum ether: dichloromethane=2:1 as mobile phase) to obtain 1.97g of white solid powder C 1 in 71% yield.
In the invention, the specific step III is as follows: to a 100mL single neck round bottom flask was added 3, 6-di-tert-butylcarbazole (0.7 g,2.5mmol,2 equiv), sodium hydride (105 mg,2.64mmol,2.1equiv,60% dispersed in mineral oil) and N, N-dimethylformamide (20 mL) and stirred at room temperature under nitrogen for 2 hours. The compound of formula B 1 (0.5 g,1.25mmol,1.0 equiv) was added slowly and the mixture was then heated to 65℃for 12 hours with stirring. After the completion of the reaction, the reaction mixture was poured into 40mL of water, allowed to stand for precipitation and filtration, and the residue was purified by column chromatography (petroleum ether: dichloromethane=2:1 as mobile phase) to obtain 1.04g of white solid powder C 2 in a yield of 90%.
The results of the nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum analysis of each intermediate product are as follows:
Intermediate products B1:Mp 172-173℃;1H NMR(400MHz,CDCl3):δ7.81(S,2H),7.70(d,J＝8.0Hz,2H);13C NMR(101MHz,CDCl3):δ159.3(d,J＝258.6Hz),132.25(t,J＝2.0Hz),125.4(d,J＝10.1Hz),125.3(d,J＝2.0Hz),124.9(d,J＝25.3Hz),124.8(d,J＝16.2Hz),121.33(d,J＝20.2Hz),116.4(t,J＝2.0Hz),114.50(t,J＝2.0Hz);HR-MS(APCI):m/z calcd for C14H3N2Br2F2 -[M-H]-394.86365,found 394.86325.
Intermediate products C1:Mp 253-257℃;1H NMR(400MHz,d6-DMSO):δ8.77(d,J＝4Hz,2H),8.09(d,J＝8Hz,2H),7.82(d,J＝4Hz,2H),7.78(d,J＝8Hz,2H),7.31(t,J＝8Hz,2H),7.24(t,J＝8Hz,2H),6.98(d,J＝8Hz,2H),6.87(t,J＝8Hz,2H),6.53(t,J＝8Hz,2H),5.39(d,J＝8Hz,2H);13C NMR(101MHz,d6-DMSO):δ141.1,139.8,139.0,138.3,137.0,135.0,126.6,126.0,125.2,124.2,123.9,121.4,121.3,121.1,120.1,118.4,117.2,108.9,108.8;HR-MS(ESI):m/zcalcd for C38H20N4Br2Na+[M-Na]+712.99469,found 712.994692.
Intermediate products C2:Mp 300-301℃;1H NMR(400MHz,CDCl3):δ8.08(d,J＝2Hz,2H),7.87(d,J＝4Hz,2H),7.63(d,J＝4Hz,2H),7.38(d,J＝2Hz,2H),7.31(dd,J＝8Hz,J＝2Hz,2H),6.89(d,J＝8Hz,2H),6.64(dd,J＝8Hz,J＝2Hz,2H),5.53(6,J＝8Hz,2H),1.43(s,9H),1.32(s,9H);13C NMR(101MHz,CDCl3):δ144.2,143.6,141.5,140.4,139.4,137.5,135.6,134.9,124.9,124.8,124.4,123.6,123.3,118.4,116.8,116.7,115.5,109.9,109.0,34.7,34.5,32.0,31.9;MALDI-MS:m/z calcd for C54H52N4Br2 914.256,found 914.092.
Example 1 preparation of Polymer of formula A
The specific reaction step IV-1 is as follows:
To a 100mL two-necked flask, compound C 1(692.4mg,1.0mmol,1.0equiv),a1 (612.2 mg,3.0mol,3.0 equiv), tetrakis (triphenylphosphine) palladium (57.8 mg,0.05mmol,0.05 equiv) and potassium carbonate (691 mg,5.0mmol,5.0 equiv) were added and the gas was evacuated three times. Degassed toluene/water (20/5 mL) was added and heated to 100deg.C for 24 hours. After the reaction, the solvent was dried under reduced pressure to obtain a crude product. The crude product was passed through a silica gel column (petroleum ether: dichloromethane=4:1 as mobile phase) to give product a (535.7 mg,0.78mmol, 78%) as a white powder.
Mass spectrometry analysis of product a: HR-MS: m/z calcd for C 50H30N4 686.2471,found 686.2474.
Example 2 preparation of Polymer of formula B
The specific reaction step IV-2 is as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 2 (1.88 g,3.0mmol,3.0 equiv.) in the original example to give product B (593.3 mg,0.83mmol, 83%) as a white solid.
Mass spectrometry analysis of product B: HR-MS (ESI) m/z calcd for C 52H34N4 714.2784,found 714.2787.
Example 3 preparation of Polymer of formula C
The specific reaction step IV-3 is as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 3 (702.3 mg,3.0mmol,3.0 equiv.) in the original example to give product C as a white solid (567.6 mg,0.76mmol, 76%).
Mass spectrometry analysis of product C: HR-MS (ESI) m/z calcd for C 52H34N4O2 746.2682,found 746.2686.
Example 4 preparation of Polymer of formula D
The specific reaction step IV-4 is as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 4 (657.3 mg,3.0mmol,3.0 equiv.) in the original example to give product D (559.1 mg,0.78mmol, 78%) as a yellow solid.
Mass spectrometry analysis of product D: HR-MS (ESI) m/z calcd for C 50H32N6 716.2688,found 716.2697.
Example 5 preparation of Polymer of formula E
The specific reaction step IV-5 is as follows:
This example was synthesized essentially the same as compound a 1, except that a 5 (729.3 mg,3.0mmol,3.0 equiv) was substituted for a 1 in the original example to give product E (527.8 mg,0.69mmol, 69%) as a yellow solid.
Mass spectrometry analysis of product E: HR-MS (ESI) m/z calcd for C 54H32N6 764.2688,found 764.2697.
Example 6 preparation of Polymer of formula F
The specific reaction step IV-6 is as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 6 (696.3 mg,3.0mmol,3.0 equiv) in the original example to give product F (609.1 mg,0.82mmol, 82%) as a yellow solid.
Mass spectrometry analysis of product F: HR-MS (ESI) m/z calcd for C 52H30N4O2 742.2369,found 742.2376.
Example 7 preparation of Polymer of formula G
The specific reaction step IV-7 is as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 7 (786.3 mg,3.0mmol,3.0 equiv.) in the original example to give product G (521.9 mg,0.65mmol, 65%) as a yellow solid.
Mass spectrometry analysis of product G: HR-MS (ESI) m/z calcd for C 54H34N4O4 802.2580,found 802.2594.
Example 8 preparation of Polymer of formula H
The specific reaction steps IV-88 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 8 (924.6 mg,3.0mmol,3.0 equiv.) in the original example to give product H (698.1 mg,0.78mmol, 78%) as a yellow solid.
Mass spectrometry analysis of product H: HR-MS (ESI) m/z calcd for C 64H38N4O2 894.2995,found 894.3017.
Example 9 preparation of Polymer of formula I
The specific reaction step IV-9 is as follows:
this example was synthesized essentially the same as compound A, except that a 1 was replaced with a 9 (654.3 mg,3.0mmol,3.0 equiv.) in the original example to give product I as a yellow solid (529.0 mg,0.74mmol, 74%).
Mass spectrometry analysis of product I: HR-MS (ESI) m/z calcd for C 52H34N4 714.2783,found 714.2797.
Example 10 preparation of Polymer of formula J
The specific reaction steps IV-10 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 10 (654.3 mg,3.0mmol,3.0 equiv.) in the original example to give product J as a yellow solid (471.8 mg,0.66mmol, 66%).
Mass spectrometry analysis of product J: HR-MS (ESI) m/z calcd for C 52H34N4 714.2783,found 714.2794.
Example 11 preparation of Polymer of formula K
The specific reaction steps IV-11 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 11 (738.5 mg,3.0mmol,3.0 equiv.) to give product K (408.6 mg,0.53mmol, 53%) as a yellow solid.
Mass spectrometry analysis of product K: HR-MS (ESI) m/z calcd for C 56H42N4 770.3409,found 770.3422.
Example 12 preparation of Polymer of formula L
The specific reaction steps IV-12 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 12 (702.3 mg,3.0mmol,3.0 equiv.) in the original example to give product L (642.3 mg,0.86mmol, 86%) as a yellow solid.
Mass spectrometry analysis of product L: HR-MS (ESI) m/z calcd for C 52H34N4O2 746.2682,found 746.2696.
Example 14 preparation of Polymer of formula M
The specific reaction steps IV-13 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 13 (702.3 mg,3.0mmol,3.0 equiv.) in the original example to give product M (552.7 mg,0.74mmol, 74%) as a yellow solid.
Mass spectrometry analysis of product M: HR-MS (ESI) m/z calcd for C 52H34N4O2 746.2682,found 746.2693.
Example 15 preparation of Polymer of formula N
The specific reaction steps IV-14 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 14 (792.4 mg,3.0mmol,3.0 equiv.) in the original example to give product N (621.3 mg,0.77mmol, 77%) as a yellow solid.
Mass spectrometry analysis of product N: HR-MS (ESI) m/z calcd for C 54H38N4O4 806.2893,found 806.2904.
Example 16 preparation of Polymer of formula O
The specific reaction steps IV-15 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 15 (882.5 mg,3.0mmol,3.0 equiv.) in the original example to give product O as a yellow solid (505.6 mg,0.57mmol, 57%).
Mass spectrometry analysis of product O: HR-MS (ESI) m/z calcd for C 56H42N4O6 886.3104,found 886.3117.
Example 17 preparation of Polymer of formula P
The specific reaction steps IV-16 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 16 (657.3 mg,3.0mmol,3.0 equiv) in the original example to give product P (638.0 mg,0.89mmol, 89%) as a yellow solid.
Mass spectrometry analysis of product P: HR-MS (ESI) m/z calcd for C 50H32N6 716.2688,found 716.2697.
Example 18 preparation of Polymer of formula Q
The specific reaction steps IV-17 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 17 (657.3 mg,3.0mmol,3.0 equiv.) in the original example to give product Q (523.3 mg,0.73mmol, 73%) as a yellow solid.
Mass spectrometry analysis of product Q: HR-MS (ESI) m/z calcd for C 50H32N6 716.2688,found 716.2691.
Example 19 preparation of Polymer of formula R
The specific reaction steps IV-18 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 18 (687.3 mg,3.0mmol,3.0 equiv.) in the original example to give the product R as a yellow solid (648.4 mg,0.88mmol, 88%).
Mass spectrometry analysis of product R: HR-MS (ESI) m/z calcd for C 52H28N6 736.2375,found 736.2387.
Example 20 preparation of Polymer of formula S
The specific reaction steps IV-19 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 19 (687.3 mg,3.0mmol,3.0 equiv) in the original example to give the product S as a yellow solid (523.2 mg,0.71mmol, 71%).
Mass spectrometry analysis of product S: HR-MS (ESI) m/z calcd for C 52H28N6 736.2375,found 736.2389.
Example 21 preparation of Polymer of formula T
The specific reaction steps IV-20 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 20 (762.3 mg,3.0mmol,3.0 equiv.) in the original example to give product T (668.8 mg,0.85mmol, 85%) as a yellow solid.
Mass spectrometry analysis of product T: HR-MS (ESI) m/z calcd for C 54H26N8 786.2280,found 786.2298.
Example 21 preparation of Polymer of formula U
The specific reaction steps IV-21 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 21 (837.3 mg,3.0mmol,3.0 equiv.) in the original example to give the product U as a yellow solid (393.3 mg,0.47mmol, 47%).
Mass spectrometry analysis of product U: HR-MS (ESI) m/z calcd for C 56H24N10 836.2185,found 836.2198.
Example 22 preparation of Polymer of formula V
The specific reaction steps IV-22 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 22 (786.3 mg,3.0mmol,3.0 equiv.) in the original example to give product V (698.5 mg,0.87mmol, 87%) as a yellow solid.
Mass spectrometry analysis of product V: HR-MS (ESI) m/z calcd for C 54H34N4O4 802.2580,found 802.2591.
Example 23 preparation of Polymer of formula W
The specific reaction steps IV-23 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 23 (786.3 mg,3.0mmol,3.0 equiv) in the original example to give product W (578.1 mg,0.72mmol, 72%) as a yellow solid.
Mass spectrometry analysis of product W: HR-MS (ESI) m/z calcd for C 54H34N4O4 802.2580,found 802.2591.
Example 24 preparation of Polymer of formula X
The specific reaction steps IV-24 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 24 (837.3 mg,3.0mmol,3.0 equiv.) in the original example to give product X (393.3 mg,0.47mmol, 47%) as a yellow solid.
Mass spectrometry analysis of product X: HR-MS (ESI) m/z calcd for C 56H24N10 836.2185,found 836.2198.
Example 25 preparation of Polymer of formula Y
The specific reaction steps IV-25 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 25 (924.6 mg,3.0mmol,3.0 equiv.) in the original example to give the product Y as a yellow solid (689.2 mg,0.77mmol, 77%).
Mass spectrometry analysis of product Y: HR-MS (ESI) m/z calcd for C 64H38N4O2 894.2995,found 894.3014.
Example 26 preparation of Polymer of formula Z
The specific reaction steps IV-26 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 26 (762.4 mg,3.0mmol,3.0 equiv) in the original example to give product Z as a yellow solid (708.2 mg,0.90mmol, 90%).
Mass spectrometry analysis of product Z: HR-MS (ESI) m/z calcd for C 58H34N4 786.2783,found 786.2795.
Example 27 preparation of Polymer of formula AA
The specific reaction steps IV-27 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 27 (762.4 mg,3.0mmol,3.0 equiv.) in the original example to give product AA (637.4 mg,0.81mmol, 81%) as a yellow solid.
Mass spectrometry analysis of product AA: HR-MS (ESI) m/z calcd for C 58H34N4 786.2783,found 786.2799.
Example 28 preparation of Polymer of formula AB
The specific reaction steps IV-28 are as follows:
This example was synthesized essentially the same as compound A, except that a 1 was replaced with a 28 (912.6 mg,3.0mmol,3.0 equiv.) in the original example to give product AB as a yellow solid (727.4 mg,0.82mmol, 82%).
Mass spectrometry analysis of product AB: HR-MS (ESI) m/z calcd for C 66H38N4 886.3096,found 886.3108.
Example 29 preparation of Polymer of formula AC
The specific reaction steps IV-29 are as follows:
This example was synthesized essentially the same as compound a, except that a 1 was replaced with a 29 (912.6 mg,3.0mmol,3.0 equiv) in the original example to give the product AC as a yellow solid (576.6 mg,0.65mmol, 65%).
Mass spectrometry analysis of product AC: HR-MS (ESI) m/z calcd for C 66H38N4 886.3096,found 886.3115.
Example 30 preparation of Polymer of formula AD
The specific reaction steps IV-30 are as follows:
this example was synthesized essentially the same as compound a, except that a 1 was replaced with a 30 (912.6 mg,3.0mmol,3.0 equiv) in the original example to give the product AD (656.4 mg,0.74mmol, 74%) as a yellow solid.
Mass spectrometry analysis of product AD: HR-MS (ESI) m/z calcd for C 66H38N4 886.3096,found 886.3099.
Example 31 preparation of Polymer of formula AE
The specific reaction steps IV-31 are as follows:
To a 100mL schlenk tube was added compound C 1 (692.4 mg,1.0mmol,1.0 equiv), tris (dibenzylideneacetone) dipalladium (45.8 mg,0.05mmol,0.05 equiv), sodium t-butoxide (480.5 mg,5.0mmol,5.0 equiv), a 31 (627.9 mg,3.0mmol,3.0 equiv). Moving to the glove box, tri-t-butylphosphine (0.2 mL,0.15equiv,10% in toluene) and dry toluene solvent (30 mL) were added. Screw plugs were screwed and removed from the glove box and stirred with heating at 110 ℃ for 12 hours. After the reaction, the solvent was dried under reduced pressure to obtain a crude product. The crude product was passed through a silica gel column (petroleum ether: dichloromethane=5:1 as mobile phase) to give AE (873.2 mg,0.92mmol, 92%) as a yellowish green solid.
Mass spectrometry results for example AE: HR-MS (ESI) m/z calcd for C 68H48N6 948.3940,found 948.3955.
Example 32 preparation of Polymer shown in AF
The specific reaction steps IV-32 are as follows:
This example was synthesized essentially the same as compound AE, except that a 31 was changed to a 32 (549.6 mg,3.0mmol,3.0 equiv) in the original example to give the product AF as a yellowish green solid (798.3 mg,0.89mmol, 89%).
Mass spectrometry results for example AF: HR-MS (ESI) m/z calcd for C 62H36N6O2 896.2900,found 896.2911.
Example 33 preparation of Polymer of formula AG
The specific reaction steps IV-33 are as follows:
This example was synthesized essentially the same as compound AE, except that a 31 was changed to a 33 (597.8 mg,3.0mmol,3.0 equiv) in the original example to give the product AG as a yellowish green solid (780.5 mg,0.84mmol, 84%).
Mass spectrometry results for example AG: HR-MS (ESI) m/z calcd for C 62H36N6S2 928.2443,found 928.2458.
Example 34 preparation of Polymer shown as AH
The specific reaction step V-1 is as follows:
To a 100mL two-necked flask, compound C 2(916.8mg,1.0mmol,1.0equiv),a1 (612.2 mg,3.0mol,3.0 equiv), tetrakis (triphenylphosphine) palladium (57.8 mg,0.05mmol,0.05 equiv) and potassium carbonate (691 mg,5.0mmol,5.0 equiv) were added and the gas was evacuated three times. Degassed toluene/water (20/5 mL) was added and heated to 100deg.C for 24 hours. After the reaction, the solvent was dried under reduced pressure to obtain a crude product. The crude product was passed through a silica gel column (petroleum ether: dichloromethane=4:1 as mobile phase) to give product AH (665.2 mg,0.73mmol, 73%) as a white powder.
Mass spectrometry analysis of product AH: HR-MS: m/z calcd for C 66H62N4 910.4974,found 910.4988.
Example 34 preparation of Polymer shown as AH
The specific reaction step V-2 is as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 2 (1.88 g,3.0mmol,3.0 equiv) to give the product AI as a white solid (742.1 mg,0.79mmol, 79%).
Mass spectrometry analysis of product AI: HR-MS (ESI) m/z calcd for C 68H66N4 938.5287,found 938.5298.
Example 35 preparation of Polymer of formula AJ
The specific reaction step V-3 is as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 3 (702.3 mg,3.0mmol,3.0 equiv.) in the original example to give the product AJ as a white solid (747.9 mg,0.77mmol, 77%).
Mass spectrometry analysis of product AJ: HR-MS (ESI) m/z calcd for C 68H66N4O2 970.5186,found 970.5197.
Example 35 preparation of Polymer of formula AK
The specific reaction step V-4 is as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 4 (657.3 mg,3.0mmol,3.0 equiv) in the original example to give the yellow solid product AK (559.1 mg,0.78mmol, 78%).
Mass spectrometry analysis of product AK: HR-MS (ESI) m/z calcd for C 66H64N6 940.5192,found 940.5203.
Example 35 preparation of Polymer of formula AL
The specific reaction step V-5 is as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 5 (729.3 mg,3.0mmol,3.0 equiv.) in the original example to give the product AL as a yellow solid (751.9 mg,0.76mmol, 76%).
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Mass spectrometry analysis of product E: HR-MS (ESI) m/z calcd for C 70H64N6 988.5192,found 988.5208.
Example 36 preparation of Polymer of formula AM
The specific reaction step V-6 is as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 6 (696.3 mg,3.0mmol,3.0 equiv.) to give the product AM as a yellow solid (802.8 mg,0.83mmol, 83%).
Mass spectrometry analysis of product AM: HR-MS (ESI) m/z calcd for C 68H62N4O2 966.4873,found 966.4889.
Example 37 preparation of Polymer of formula AN
The specific reaction step V-7 is as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 7 (786.3 mg,3.0mmol,3.0 equiv.) in the original example to give product AN (883.5 mg,0.65mmol, 86%) as a yellow solid.
Mass spectrometry analysis of product AN: HR-MS (ESI) m/z calcd for C 70H66N4O4 1026.5084,found 1026.5097.
Example 38 preparation of Polymer of formula AO
The specific reaction step V-8 is as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 8 (924.6 mg,3.0mmol,3.0 equiv.) to give product AO (973.9 mg,0.87mmol, 87%) as a yellow solid.
Mass spectrometry analysis of product AO: HR-MS (ESI) m/z calcd for C 80H70N4O2 1118.5499,found 1118.5513.
Example 39 preparation of Polymer of formula AP
The specific reaction step V-9 is as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 9 (654.3 mg,3.0mmol,3.0 equiv) in the original example to give product AP (666.9 mg,0.71mmol, 71%) as a yellow solid.
Mass spectrometry analysis of product AP: HR-MS (ESI) m/z calcd for C 68H66N4 938.5287,found 938.5298.
Example 40 preparation of Polymer of formula AQ
The specific reaction step V-10 is as follows:
This example is essentially identical to the synthesis of compound AH, except that a 1 is replaced with a 10 (654.3 mg,3.0mmol,3.0 equiv) in the original example, yielding product AQ (666.9 mg,0.71mmol, 71%) as a yellow solid.
Mass spectrometry analysis of product AQ: HR-MS (ESI) m/z calcd for C 68H66N4 938.5287,found 938.5298.
Example 41 preparation of Polymer of formula AR
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 11 (738.5 mg,3.0mmol,3.0 equiv.) to give the product AR (487.8 mg,0.49mmol, 49%) as a yellow solid.
Mass spectrometry analysis of product AR: HR-MS (ESI) m/z calcd for C 72H74N4 994.5913,found 994.5926.
Example 42 preparation of Polymer of formula AS
The specific reaction step V-12 is as follows:
This example was synthesized essentially the same AS compound AH, except that a 1 was replaced with a 12 (702.3 mg,3.0mmol,3.0 equiv.) in the original example to give the product AS AS a yellow solid (825.6 mg,0.85mmol, 85%).
Mass spectrometry analysis of product AS: HR-MS (ESI) m/z calcd for C 68H66N4O2 970.5186,found 970.5198.
Example 43 preparation of Polymer of formula AT
The specific reaction step V-13 is as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 13 (702.3 mg,3.0mmol,3.0 equiv) to give product AT (641.1 mg,0.66mmol, 66%) as a yellow solid.
Mass spectrometry analysis of product AT: HR-MS (ESI) m/z calcd for C 68H66N4O2 970.5186,found 970.5204.
Example 44 preparation of Polymer of formula AU
The specific reaction step V-14 is as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 14 (792.4 mg,3.0mmol,3.0 equiv) in the original example to give the product AU (752.9 mg,0.73mmol, 73%) as a yellow solid.
Mass spectrometry analysis of product AU: HR-MS (ESI) m/z calcd for C 70H70N4O4 1030.5397,found 1030.5411.
Example 45 preparation of Polymer of formula AV
The specific reaction step V-15 is as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 15 (882.5 mg,3.0mmol,3.0 equiv.) to give the product AV as a yellow solid (447.5 mg,0.41mmol, 41%).
Mass spectrometry analysis of product AV: HR-MS (ESI) m/z calcd for C 72H74N4O6 1090.5608,found 1090.5617.
Preparation of Polymer of example 46, formula AW
The specific reaction step V-16 is as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 16 (657.3 mg,3.0mmol,3.0 equiv) in the original example to give the yellow solid product AW (800.1 mg,0.85mmol, 85%).
Mass spectrometry analysis of product AW: HR-MS (ESI) m/z calcd for C 66H64N6 940.5192,found 940.5207.
Example 47 preparation of Polymer of formula AX
The specific reaction steps V-17 are as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 17 (657.3 mg,3.0mmol,3.0 equiv.) to give the product AX as a yellow solid (593.0 mg,0.63mmol, 63%).
Mass spectrometry analysis of product AX: HR-MS (ESI) m/z calcd for C 66H64N6 940.5192,found 940.5215.
Example 48 preparation of Polymer of formula AY
The specific reaction steps V-18 are as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 18 (687.3 mg,3.0mmol,3.0 equiv.) in the original example to give the product AY as a yellow solid (778.6 mg,0.81mmol, 81%).
Mass spectrometry analysis of product AY: HR-MS (ESI) m/z calcd for C 68H60N6 960.4879,found 960.4887.
Example 49 preparation of Polymer of formula AZ
The specific reaction steps V-19 are as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 19 (687.3 mg,3.0mmol,3.0 equiv) in the original example to give AZ (596.0 mg,0.62mmol, 62%) as a yellow solid powder.
Mass spectrometry of product AZ: HR-MS (ESI) m/z calcd for C 68H60N6 960.4879,found 960.4887.
Example 50 preparation of Polymer of formula BA
The specific reaction step V-20 is as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 20 (762.3 mg,3.0mmol,3.0 equiv) in the original example to give the product BA as a yellow solid (819.1 mg,0.81mmol, 81%).
Mass spectrometry analysis of product BA: HR-MS (ESI) m/z calcd for C 70H58N8 1010.4784,found 1010.4798.
Example 51 preparation of Polymer shown in BB
The specific reaction step V-21 is as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 21 (837.3 mg,3.0mmol,3.0 equiv.) in the original example to give the yellow solid product BB (435.1 mg,0.41mmol, 41%).
Mass spectrometry analysis of product BB: HR-MS (ESI) m/z calcd for C 72H56N10 1060.4689,found 1060.4697.
Example 52 preparation of Polymer shown in BC
The specific reaction step V-22 is as follows:
this example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 22 (786.3 mg,3.0mmol,3.0 equiv.) to give product BC (852.7 mg,0.83mmol, 83%) as a yellow solid.
Mass spectrometry analysis of product BC: HR-MS (ESI) m/z calcd for C 70H66N4O4 1026.5084,found 1026.5097.
Example 53 preparation of Polymer of formula BD
The specific reaction steps V-23 are as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 23 (786.3 mg,3.0mmol,3.0 equiv) in the original example to give the product BD as a yellow solid (688.3 mg,0.67mmol, 67%).
Mass spectrometry analysis of product BD: HR-MS (ESI) m/z calcd for C 70H66N4O4 1026.5084,found 1026.5091.
Example 54 preparation of Polymer of formula BE
The specific reaction steps V-24 are as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 24 (837.3 mg,3.0mmol,3.0 equiv) in the original example to give the product BE (839.6 mg,0.75mmol, 75%) as a yellow solid.
Mass spectrometry analysis of product BE: HR-MS (ESI) m/z calcd for C 80H70N4O2 1118.5499,found 1118.5521.
Example 55 preparation of Polymer of formula BF
The specific reaction step V-25 is as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 25 (924.6 mg,3.0mmol,3.0 equiv) in the original example to give the product BF as a yellow solid (716.5 mg,0.64mmol, 64%).
Mass spectrometry analysis of product BF: HR-MS (ESI) m/z calcd for C 80H70N4O2 1118.5499,found 1118.5527.
Example 56 preparation of Polymer of formula BG
The specific reaction steps V-26 are as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 26 (762.4 mg,3.0mmol,3.0 equiv) to give the product BG as a yellow solid (890.0 mg,0.88mmol, 88%).
Mass spectrometry analysis of product BG: HR-MS (ESI) m/z calcd for C 74H66N4 1010.5287,found 1010.5298.
Example 57 preparation of Polymer of formula BH
The specific reaction steps V-27 are as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 27 (762.4 mg,3.0mmol,3.0 equiv) in the original example to give product BH (738.3 mg,0.73mmol, 73%) as a yellow solid.
Mass spectrometry analysis of product BH: HR-MS (ESI) m/z calcd for C 74H66N4 1010.5287,found 1010.5293.
Example 58 preparation of Polymer of formula BI
The specific reaction steps V-28 are as follows:
This example is essentially identical to the synthesis of compound AH, except that a 1 is replaced with a 28 (912.6 mg,3.0mmol,3.0 equiv) in the original example, yielding the product BI as a yellow solid (789.2 mg,0.71mmol, 71%).
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Mass spectrometry results for product BI: HR-MS (ESI) m/z calcd for C 82H70N4 1110.5600,found 1110.5624.
Example 59 preparation of Polymer shown in BJ
The specific reaction steps V-29 are as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 29 (912.6 mg,3.0mmol,3.0 equiv) to give product BJ (622.4 mg,0.56mmol, 56%) as a yellow solid.
Mass spectrometry analysis of product BJ: HR-MS (ESI) m/z calcd for C 82H70N4 1110.5600,found 1110.5619.
Example 60 preparation of Polymer of formula BK
The specific reaction steps V-30 are as follows:
This example was synthesized essentially the same as compound AH, except that a 1 was replaced with a 30 (912.6 mg,3.0mmol,3.0 equiv.) to give the product BK (477.9 mg,0.43mmol, 43%) as a yellow solid.
Mass spectrometry analysis of product BK: HR-MS (ESI) m/z calcd for C 82H70N4 1110.5600,found 1110.5611.
Example 61 preparation of Polymer shown in BL
The specific reaction step V-31 is as follows:
To a 100mL schlenk tube was added compound C 2 (916.8 mg,1.0mmol,1.0 equiv), tris (dibenzylideneacetone) dipalladium (45.8 mg,0.05mmol,0.05 equiv), sodium tert-butoxide (480.5 mg,5.0mmol,5.0 equiv), a 31 (627.9 mg,3.0mmol,3.0 equiv). Moving to the glove box, tri-t-butylphosphine (0.2 mL,0.15equiv,10% in toluene) and dry toluene solvent (30 mL) were added. Screw plugs were screwed and removed from the glove box and stirred with heating at 110 ℃ for 12 hours. After the reaction, the solvent was dried under reduced pressure to obtain a crude product. The crude product was passed through a silica gel column (petroleum ether: dichloromethane=6:1 as mobile phase) to give the product BL as a yellowish green solid (1032.8 mg,0.88mmol, 88%).
Mass spectrometry results for example BL: HR-MS (ESI) m/z calcd for C 84H80N6 1172.6444,found 1172.6453.
Example 62 preparation of Polymer shown in BM
The specific reaction step V-32 is as follows:
This example was synthesized essentially the same as compound BM, except that a 31 was changed to a 32 (549.6 mg,3.0mmol,3.0 equiv) in the original example to give the product BM as a yellowish green solid (908.4 mg,0.81mmol, 81%).
Mass spectrometry results for example BM: HR-MS (ESI) m/z calcd for C 78H68N6O2 1120.5404,found 1120.5419.
The prepared example A-BM of the present invention was dissolved in chromatographically pure toluene to prepare a diluted solution having a concentration of 10 -5 mol/L, and the photophysical properties of each diluted solution were tested. The maximum absorption wavelength, maximum emission wavelength, phosphorescent lifetime, and long persistence in liquid nitrogen are shown in table 1. The phosphorescent lifetime decay curve and long afterglow photograph of compound E in liquid nitrogen are demonstrated in FIG. 1. As can be seen from the results of Table 1 and FIG. 1, the series of aromatic hydrocarbon derivatives based on biphenyl structure all show long phosphorescence lifetime (1.44-3.29 s) and long afterglow time (18-40 s) at low temperature.
TABLE 1 photophysical Properties of Compounds A-BM
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The invention obtains a series of small molecules with low-temperature long afterglow property through C-C coupling and C-N coupling reactions. The special organic small molecules can emit phosphorescence with extremely strong and extremely long service life under the extremely low temperature environment (liquid nitrogen). After the excitation light source is turned off, the light is continuously emitted for 18-40 s. From photophysical process analysis, such materials exhibit fast intersystem crossing rates and slow phosphorescent radiation transition rates, the faster the intersystem crossing rates, the slower the phosphorescent radiation transition rates, and longer afterglow phenomena at low temperatures. Based on this particular property, such materials have many potential applications in very low temperature environments such as optical encryption, bio-imaging, and the like.
Claims (8)
1. An aromatic hydrocarbon derivative based on a biphenyl structure, the structural formula of which is shown as a formula TM;
In formula TM, the radical donor is an electron-rich donor radical selected from any of the following radicals:
The group X is simultaneously selected from any one of structures shown in a 1～a33;
2. the process for producing a biphenyl structure-based aromatic hydrocarbon derivative according to claim 1, comprising the steps of:
1) Amidating the compound shown in the formula A 1 with sulfonamide and dehydrating to obtain a compound shown in the formula B 1;
2) In the presence of sodium hydride, carrying out nucleophilic substitution reaction on a compound shown in a formula B 1 and a compound corresponding to an electron donating group donor to respectively obtain a compound shown in a formula C 1 and a compound shown in a formula C 2;
The electron donating group donor is an electron rich donor group selected from carbazole and 3, 6-di-tert-butylcarbazole;
3) Carrying out Suzuki coupling reaction or Buchwald-Hartwig coupling reaction on a compound shown in a formula C 1 or a compound shown in a formula C 2 and a compound corresponding to a group X to obtain an aromatic hydrocarbon derivative with a biphenyl structure shown in a formula TM;
the definition of the group X is the same as the formula TM.
3. The preparation method according to claim 2, characterized in that: in step 1), the amidation reaction and the dehydration reaction are carried out in sulfolane;
The molar ratio of the compound represented by formula a 1 to the sulfonamide is 1:2 to 4;
the course of the reaction is as follows: reacting for 3-4 hours at 160 ℃;
No inert gas is needed for protection.
4. A method of preparation according to claim 2 or 3, characterized in that: in step 2), the nuclear substitution reaction is carried out as follows:
Stirring a compound shown in a formula B 1 and sodium hydride in dry N, N-dimethylformamide at room temperature for 0.5-1 hour, then adding a compound corresponding to the radical donor, and reacting for 10-12 hours at 60-80 ℃;
The molar ratio of the compound shown in the formula B 1 to the compound corresponding to the group donor is 1:1.1 to 1.2:1.9 to 2;
An inert gas blanket is required.
5. A method of preparation according to claim 2 or 3, characterized in that: in the step 3), the conditions of the Suzuki coupling reaction are as follows:
In the presence of tetrakis (triphenylphosphine) palladium and potassium carbonate;
The molar ratio of the compound shown in the formula C 1 or the compound shown in the formula C 2, the compound corresponding to the group X, the tetra (triphenylphosphine) palladium and the potassium carbonate is 1:1 to 1.05:0.05 to 0.1:5 to 8;
The solvent is a mixed solution of toluene and water, and the volume ratio is 1:0.3 to 0.5;
The reaction temperature is 105-110 ℃;
the reaction time is 20-24 hours;
An inert gas blanket is required.
6. A method of preparation according to claim 2 or 3, characterized in that: in step 3), the conditions for the Buchwald-Hartwig coupling reaction are as follows:
In the presence of tris (dibenzylideneacetone) dipalladium and sodium tert-butoxide;
The molar ratio of the compound shown in the formula C 1 or the compound shown in the formula C 2, the compound corresponding to the group X, the tris (dibenzylideneacetone) dipalladium to the sodium tert-butoxide is 1:1 to 1.05:0.05 to 0.1:5 to 8;
The solvent is dry toluene;
The reaction temperature is 105-110 ℃;
the reaction time is 20-24 hours;
An inert gas blanket is required.
7. Use of the aromatic hydrocarbon derivative based on biphenyl structure according to claim 1 as or for preparing organic luminescent material.
8. The application of the aromatic hydrocarbon derivative based on the biphenyl structure in anti-counterfeiting encryption, biological imaging and optical temperature probes as claimed in claim 1;
The application is for the purpose of diagnosis and treatment of non-diseases.
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| CN109535420A (en) * | 2018-11-14 | 2019-03-29 | 武汉华星光电半导体显示技术有限公司 | A kind of dark red smooth high molecular material of thermal activation delayed fluorescence and preparation method thereof |
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| CN109535420A (en) * | 2018-11-14 | 2019-03-29 | 武汉华星光电半导体显示技术有限公司 | A kind of dark red smooth high molecular material of thermal activation delayed fluorescence and preparation method thereof |
| CN115260455A (en) * | 2022-08-23 | 2022-11-01 | 中国科学院化学研究所 | Low-temperature long-afterglow polymer based on biphenyl structure and preparation method thereof |
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| An axially chiral thermally activated delayed fluorescent emitter with a dual emitting core for a highly efficient organic light-emitting diode;Yin-Feng Wang等;《Chemical Communications》;第56卷(第65期);第9380-9383页 * |
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