CN115504926A - Novel low-temperature ultra-long afterglow molecular material and preparation method thereof - Google Patents
Novel low-temperature ultra-long afterglow molecular material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims description 77
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 29
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- -1 2-substituted benzene ring Chemical group 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 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
- 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 11
- 239000002904 solvent Substances 0.000 claims description 9
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000012312 sodium hydride Substances 0.000 claims description 8
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 8
- 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 7
- 229910000027 potassium carbonate 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- HJCUTNIGJHJGCF-UHFFFAOYSA-N 9,10-dihydroacridine Chemical compound C1=CC=C2CC3=CC=CC=C3NC2=C1 HJCUTNIGJHJGCF-UHFFFAOYSA-N 0.000 claims description 4
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 4
- 150000001555 benzenes Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
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- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- 150000003456 sulfonamides Chemical class 0.000 claims description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 2
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 230000002862 amidating effect Effects 0.000 claims description 2
- 238000007112 amidation reaction Methods 0.000 claims description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 2
- 229950000688 phenothiazine Drugs 0.000 claims description 2
- 125000005581 pyrene group Chemical group 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 239000000523 sample Substances 0.000 claims description 2
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- 238000006467 substitution reaction Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 64
- 238000003786 synthesis reaction Methods 0.000 abstract description 64
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- 235000010290 biphenyl Nutrition 0.000 abstract description 13
- 239000004305 biphenyl Substances 0.000 abstract description 13
- 150000001492 aromatic hydrocarbon derivatives Chemical class 0.000 abstract description 11
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- 230000005283 ground state Effects 0.000 abstract description 4
- 239000011368 organic material Substances 0.000 abstract description 4
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- 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
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- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 230000009435 amidation Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
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- 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
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- 238000004020 luminiscence type Methods 0.000 description 1
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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
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- 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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- 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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- 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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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1018—Heterocyclic 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 in a formula TM. The low-temperature ultra-long afterglow molecular material provided by the invention is a series of pure organic materials, wherein each organic material has an extremely fast intersystem crossing rate (from a first singlet state to a triplet state) and an extremely slow phosphorescence radiation rate (from a first triplet state to a ground state), and macroscopically shows that the material emits light continuously for 18-40 seconds at low temperature. The method for preparing the aromatic hydrocarbon derivative based on the biphenyl structure has the advantages of cheap and easily obtained raw materials and simple synthesis stepsHigh efficiency, 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 prospect in the field of continuous luminescent materials.
Description
Technical Field
The invention relates to a novel low-temperature ultra-long afterglow molecular material and a preparation method thereof, belonging to the field of organic luminescent material chemistry.
Background
The ultra-long afterglow material in the extremely low temperature environment is a material with special phenomena and potential application. The material can emit extremely strong phosphorescence with extremely long service life after photoexcitation in an extremely low temperature environment. After the excitation light source is closed, the light can continuously emit for 20 to 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 radiative transition rates (from the first triplet state to the ground state) at very low temperatures. Thus, after 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 and the slower the phosphorescent radiation transition rate of such materials, the longer the afterglow at low temperatures. Based on the special property, the material has a plurality of potential applications in extremely low temperature environment, such as encryption anti-counterfeiting, biological imaging and optical temperature probes.
Disclosure of Invention
The invention aims to provide a biphenyl structure-based ultra-long low-temperature afterglow material, wherein each molecule of the material shows thermal activation delayed fluorescence property and ultra-long low-temperature long afterglow phenomenon, and the material is a special functional material further used in an extremely 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, a group donor is an electron-rich donor group and is selected from carbazole and 3, 6-di-tert-butylcarbazole;
the group X is selected from benzene rings, substituted benzene rings, naphthalene rings, perylene rings, pyrene rings, 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, a 3, 5-disubstituted benzene ring and a 2,4, 6-trisubstituted benzene ring, wherein the substituent is any one of methyl, methoxy, amino, cyano, aldehyde group, ester group and phenylcarbonyl.
The arene derivative with a 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) Formula A 1 Amidating and dehydrating the compound with sulfamide to obtain the formula B 1 A compound shown in the specification;
the method can efficiently convert carboxylic acid into cyano group under the condition that bromine atoms and fluorine atoms on a benzene ring are not damaged;
2) Formula B 1 The compound firstly reacts with sodium hydride and then reacts with a compound corresponding to an electron-donating group donor to obtain a compound shown as a formula C 1 A compound shown in the specification;
the charge ratio is controlled well, wherein the electron-donating group donor can preferentially and efficiently react with the strong electron-withdrawing fluorine atom on the benzene ring and cannot react with the bromine atom on the benzene ring.
The electron-donating group donor is an electron-rich donor group and is selected from carbazole and 3, 6-di-tert-butyl carbazole;
3) Formula C 1 Carrying out Suzuki coupling reaction or Buchwald-Hartwig coupling reaction on the compound and a compound corresponding to the group X under the catalysis of a palladium catalyst and alkali to obtain an aromatic hydrocarbon derivative with a biphenyl structure shown as a formula TM;
the radical X is as defined for formula TM.
In the above production method, in step 1), the amidation and dehydration reaction is carried out in sulfolane;
formula A 1 The molar ratio of the compound to the sulfonamide is 1:2 to 1:4;
formula A 1 The compounds shown can be prepared according to the methods described in the prior art (chi.j.org.chem.2013, 33,2349.Dio 10.6023/cjoc 201306029);
the process of the electrophilic substitution reaction is as follows: firstly, reacting for 3-4 hours at 160 ℃, and then transferring to room temperature for cooling for 0.5-1 hour;
the reaction does not need inert gas protection.
In the above preparation method, in step 2), the nucleophilic substitution reaction is carried out by reacting the compound of formula B 1 Reacting the compound with sodium hydride in dry N, N-dimethylformamide at room temperature for 0.5-1 h, then adding electron-donating group donor, and continuing to react at 60-80 ℃ for 10-12 h;
the formula B 1 The molar ratio of the compound corresponding to the sodium hydride and the electron-donating group donor is 1: 1.1-1.2: 2;
the reaction requires inert gas shielding.
In the above preparation method, in step 3), the conditions of the Suzuki coupling reaction are as follows:
in the presence of tetrakis (triphenylphosphine) palladium and potassium carbonate;
formula C 1 A compound of the formula C 2 A compound shown as the formula, a compound corresponding to the group X, and the tetrakis (triphenylphosphine) palladiumThe molar ratio of the potassium carbonate to the potassium carbonate is 1:1 to 1.05: 0.05-0.1: 5 to 8 percent;
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 h;
an inert gas blanket is required.
In the above preparation method, in step 3), the conditions of the Buchwald-Hartwig coupling reaction are as follows:
in the presence of tris (dibenzylideneacetone) dipalladium and sodium tert-butoxide;
formula C 1 A compound of the formula C 2 The molar ratio of the compound shown, the compound corresponding to the group X, the tris (dibenzylideneacetone) dipalladium and the sodium tert-butoxide is 1:1 to 1.05: 0.05-0.1: 5 to 8;
the solvent is dry toluene;
the reaction temperature is 105-110 ℃;
the reaction time is 20-24 h;
an inert gas blanket is required.
The compound corresponding to the substituent X is specifically shown as the following formula a 1 -a 33 A compound shown in the specification:
the aromatic hydrocarbon derivative based on the biphenyl structure and shown in the formula TM is a series of pure organic materials, wherein each organic material has an extremely fast intersystem crossing rate (from a first singlet state to a triplet state) and an extremely slow phosphorescence radiation rate (from a first triplet state to a ground state), and macroscopically shows that the aromatic hydrocarbon derivative based on the biphenyl structure and shown by 18-40 seconds of continuous luminescence at low temperature.
The method for preparing the aromatic hydrocarbon derivative based on the biphenyl structure has the advantages of cheap 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 prospect in the field of continuous luminescent materials.
Drawings
FIG. 1 is a phosphorescence lifetime decay curve (a)) and long afterglow picture demonstration (b) of the low temperature long afterglow small molecule shown in formula E of the invention in liquid nitrogen.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
The materials, reagents and the like used in the following examples can be obtained from commercial sources or reported literatures unless otherwise specified.
The reaction route for synthesizing the biphenyl-based aromatic hydrocarbon derivative represented by the formula TM provided by the invention is as follows:
intermediate C in the invention 1 And C 2 Are key intermediates of the invention and in each case need to pass through both intermediates.
Intermediate product C 1 And C 2 The specific synthesis steps are as follows:
the method specifically comprises the following steps: adding the compound A into a 100mL two-neck round-bottom flask at room temperature 1 (4.36g, 10mmol,1.0 equiv), 30mL of thionyl chloride solvent and a catalytic amount of 4-dimethylaminopyridine (48.9mg, 0.4mmol, 0.04equiv), and then the mixture was added to reflux and stirred for 5 hours. After the reaction was completed, excess thionyl chloride was distilled off under reduced pressure, and then sulfonamide (2.88g, 30mmol,3 equiv) and sulfolane (10 mL) were added to the round-bottom flask and stirred for 3 hours while warming to 160 ℃. After the reaction was completed, it was cooled to room temperature, and 80 ml of 1 mol/l aqueous sodium hydroxide solution was added and stirred for several minutes. The precipitate was left to stand and filtered, and the residue was purified by column chromatography (mobile phase was petroleum ether: dichloromethane = 5) 1 The yield was 32%.
The method comprises the following specific steps of II: to a 100mL two-necked round-bottomed flask, carbazole (1.67g, 10mmol, 2.5equiv), sodium hydride (440mg, 11mmol,2.75equiv,60% dispersed in mineral oil) and N, N-dimethylformamide (40 mL) were added and stirred at room temperature for 2 hours under nitrogen. Slowly adding formula B 1 The compound (1.59g, 4mmol,1.0 equiv) was added, and the mixture was heated and stirred at 70 ℃ for 12 hours. After the reaction, the reaction solution was poured into 40mL of water, and the mixture was allowed to stand for precipitation and filtered, and the filter residue was purified by column chromatography (mobile phase petroleum ether: dichloromethane = 2) 1 The yield was 71%.
The method specifically comprises the following steps: to a 100mL single neck round bottom flask were added 3, 6-di-tert-butylcarbazole (0.7g, 2.5mmol, 2equiv), sodium hydride (105mg, 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. Slowly adding formula B 1 The compound (0.5g, 1.25mmol,1.0 equiv), and then the mixture was heated at 65 ℃ with stirring for 12 hours. After the reaction, the reaction solution was poured into 40mL of water, allowed to stand for precipitation and filtered, and the filter residue was purified by column chromatography (mobile phase was petroleum ether: dichloromethane =2 = 1), whereby 1.04g of a white solid powder C was obtained as a powder 2 The yield was 90%.
The nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum analysis results of each intermediate product are as follows:
intermediate B 1 :Mp 172-173℃； 1 H NMR(400MHz,CDCl 3 ):δ7.81(S,2H),7.70(d,J＝8.0Hz,2H)； 13 C NMR(101MHz,CDCl 3 ):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 C 14 H 3 N 2 Br 2 F 2 - [M-H] - 394.86365,found 394.86325.
Intermediate product C 1 :Mp 253-257℃； 1 H NMR(400MHz,d 6 -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)； 13 C NMR(101MHz,d 6 -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 C 38 H 20 N 4 Br 2 Na + [M-Na] + 712.99469,found 712.994692.
Intermediate product C 2 :Mp 300-301℃； 1 H NMR(400MHz,CDCl 3 ):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)； 13 C NMR(101MHz,CDCl 3 ):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 C 54 H 52 N 4 Br 2 914.256,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 was added 1 (692.4mg,1.0mmol,1.0equiv)，a 1 (612.2mg, 3.0mol, 3.0equiv), tetrakis (triphenylphosphine) palladium (57.8mg, 0.05mmol, 0.05equiv) and potassium carbonate (691mg, 5.0mmol, 5.0equiv) and evacuation of gas three times. Degassed toluene/water (20/5 mL) was added and heated to 100 ℃ for 24 hours. After the reaction is finished, the solvent is dried by rotary drying under reduced pressure to obtain a crude product. The crude product was passed through a silica gel column (mobile phase petroleum ether: dichloromethane = 4).
Mass spectrometry result of product a: HR-MS m/z calcd for C 50 H 30 N 4 686.2471,found 686.2474。
Example 2 preparation of Polymer of formula B
The specific reaction step IV-2 is as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 2 (1.88g, 3.0mmol,3.0 equiv) to give product B as a white solid powder (593.3 mg,0.83mmol, 83%).
Mass spectrometry results for product B: HR-MS (ESI) m/z calcd for C 52 H 34 N 4 714.2784,found 714.2787.
Example 3 preparation of Polymer of formula C
The specific reaction step IV-3 is as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 3 (702.3mg, 3.0mmol,3.0 equiv) to give product C as a white solid (567.6mg, 0.76mmol, 76%).
Mass spectrometry results for product C: HR-MS (ESI) m/z calcd for C 52 H 34 N 4 O 2 746.2682,found 746.2686.
Example 4 preparation of Polymer of formula D
The specific reaction step IV-4 is as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 4 (657.3mg, 3.0mmol, 3.0equiv) to give product D (559.1mg, 0.78mmol, 78%) as a yellow solid powder.
Mass spectrometry of product DAnd (4) fruit: HR-MS (ESI) m/z calcd for C 50 H 32 N 6 716.2688,found 716.2697.
Example 5 preparation of Polymer of formula E
The specific reaction step IV-5 is as follows:
this example and Compound A 1 The synthesis is basically the same, and the difference is that a in the original example 1 Is replaced by a 5 (729.3mg, 3.0mmol, 3.0equiv) to give product E as a yellow solid powder (527.8mg, 0.69mmol, 69%).
Mass spectrometry results for product E: HR-MS (ESI) m/z calcd for C 54 H 32 N 6 764.2688,found 764.2697.
Example 6 preparation of Polymer of formula F
The specific reaction step IV-6 is as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 6 (696.3mg, 3.0mmol, 3.0equiv) to give product F (609.1mg, 0.82mmol, 82%) as a yellow solid powder.
Mass spectrometry analysis of product F: HR-MS (ESI) m/z calcd for C 52 H 30 N 4 O 2 742.2369,found 742.2376.
Example 7 preparation of Polymer of formula G
The specific reaction step IV-7 is as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 7 (786.3mg, 3.0mmol,3.0 equiv) to give product G (521.9mg, 0.65mmol, 65%) as a yellow solid powder.
Mass spectrometry results for product G: HR-MS (ESI) m/z calcd for C 54 H 34 N 4 O 4 802.2580,found 802.2594.
Example 8 preparation of Polymer of formula H
The specific reaction steps IV-88 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 8 (924.6mg, 3.0mmol, 3.0equiv) to obtain a yellow solid powder of product H (698.1mg, 0.78mmol, 78%).
Mass spectrometry analysis of product H: HR-MS (ESI) m/z calcd for C 64 H 38 N 4 O 2 894.2995,found 894.3017.
Example 9 preparation of Polymer of formula I
The specific reaction step IV-9 is as follows:
this example is essentially the same as the synthesis of compound A, except that a is the same as in the original example 1 Is replaced by a 9 (654.3mg, 3.0mmol,3.0 equiv) to give product I (529.0 mg,0.74mmol, 74%) as a yellow solid powder.
Mass spectrometry results for product I: HR-MS (ESI) m/z calcd for C 52 H 34 N 4 714.2783,found 714.2797.
Example 10 preparation of Polymer of formula J
The specific reaction steps IV-10 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 10 (654.3mg, 3.0mmol, 3.0equiv) to obtain product J (471.8mg, 0.66mmol, 66%) as a yellow solid powder.
Mass spectrometry results for product J: HR-MS (ESI) m/z calcd for C 52 H 34 N 4 714.2783,found 714.2794.
Example 11 preparation of Polymer of formula K
The specific reaction step IV-11 is as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 11 (738.5mg, 3.0mmol, 3.0equiv) to obtain a product K (408.6mg, 0.53mmol, 53%) as a yellow solid powder.
Mass spectrometry analysis of product K: HR-MS (ESI) m/z calcd for C 56 H 42 N 4 770.3409,found 770.3422.
Example 12 preparation of Polymer of formula L
The specific reaction steps IV-12 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 12 (702.3mg, 3.0mmol, 3.0equiv) to give product L as a yellow solid powder (642.3mg, 0.86mmol, 86%).
Mass spectrometry analysis result of product L: HR-MS (ESI) m/z calcd for C 52 H 34 N 4 O 2 746.2682,found 746.2696.
Example 14 preparation of Polymer of formula M
The specific reaction steps IV-13 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 13 (702.3mg, 3.0mmol, 3.0equiv) to obtain a yellow solid product M (552.7mg, 0.74mmol, 74%) as a powder.
Mass spectrometry results of product M: HR-MS (ESI) m/z calcd for C 52 H 34 N 4 O 2 746.2682,found 746.2693.
Example 15 preparation of Polymer of formula N
The specific reaction steps IV-14 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 14 (792.4mg, 3.0mmol, 3.0equiv) to give product N (621.3mg, 0.77mmol, 77%) as a yellow solid powder.
Mass spectrometry analysis of product N: HR-MS (ESI) m/z calcd for C 54 H 38 N 4 O 4 806.2893,found 806.2904.
Example 16 preparation of Polymer of formula O
The specific reaction steps IV-15 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 15 (882.5mg, 3.0mmol, 3.0equiv) to give the product O (505.6mg, 0.57mmol, 57%) as a yellow solid powder.
Mass spectrometry analysis result of product O: HR-MS (ESI) m/z calcd for C 56 H 42 N 4 O 6 886.3104,found 886.3117.
Example 17 preparation of Polymer of formula P
The specific reaction steps IV-16 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 16 (657.3mg, 3.0mmol, 3.0equiv) to give product P (638.0mg, 0.89mmol, 89%) as a yellow solid powder.
Mass spectrometry result of product P: HR-MS (ESI) m/z calcd for C 50 H 32 N 6 716.2688,found 716.2697.
Example 18 preparation of Polymer of formula Q
The specific reaction steps IV-17 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 17 (657.3mg, 3.0mmol, 3.0equiv) to obtain product Q (523.3mg, 0.73mmol, 73%) as a yellow solid powder.
Mass spectrometry results of product Q: HR-MS (ESI) m/z calcd for C 50 H 32 N 6 716.2688,found 716.2691.
Example 19 preparation of Polymer of formula R
The specific reaction steps IV-18 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 18 (687.3mg, 3.0mmol, 3.0equiv) to give product R as a yellow solid powder (648.4mg, 0.88mmol, 88%).
Mass spectrometry results of product R: HR-MS (ESI) m/z calcd for C 52 H 28 N 6 736.2375,found 736.2387.
Example 20 preparation of Polymer of formula S
The specific reaction steps IV-19 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 19 (687.3mg, 3.0mmol, 3.0equiv) to obtain the product S (523.2mg, 0.71mmol, 71%) as a yellow solid powder.
Mass spectrometry results of product S: HR-MS (ESI) m/z calcd for C 52 H 28 N 6 736.2375,found 736.2389.
Example 21 preparation of Polymer of formula T
The specific reaction steps IV-20 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 20 (762.3mg, 3.0mmol, 3.0equiv) to give product T (668.8mg, 0.85mmol, 85%) as a yellow solid powder.
Mass spectrometry results of product T: HR-MS (ESI) m/z calcd for C 54 H 26 N 8 786.2280,found 786.2298.
Example 21 preparation of Polymer of formula U
The specific reaction steps IV-21 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 21 (837.3mg, 3.0mmol, 3.0equiv) to obtain a yellow solid powder of the product U (393.3mg, 0).47mmol,47％)。
Mass spectrometry results of product U: HR-MS (ESI) m/z calcd for C 56 H 24 N 10 836.2185,found 836.2198.
Example 22 preparation of Polymer of formula V
The specific reaction steps IV-22 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is the same as in the original example 1 Is replaced by a 22 (786.3mg, 3.0mmol, 3.0equiv) to give a product V (698.5mg, 0.87mmol, 87%) as a yellow solid powder.
Mass spectrometry result of product V: HR-MS (ESI) m/z calcd for C 54 H 34 N 4 O 4 802.2580,found 802.2591.
Example 23 preparation of Polymer of formula W
The specific reaction steps IV-23 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 23 (786.3mg, 3.0mmol, 3.0equiv) to give the product W (578.1mg, 0.72mmol, 72%) as a yellow solid powder.
Mass spectrometry analysis result of product W: HR-MS (ESI) m/z calcd for C 54 H 34 N 4 O 4 802.2580,found 802.2591.
Example 24 preparation of Polymer of formula X
The specific reaction steps IV-24 are as follows:
this implementationExample A is substantially the same as the synthesis of Compound A, except that a is the same as in the original example 1 Is replaced by a 24 (837.3mg, 3.0mmol, 3.0equiv) to obtain a product X (393.3mg, 0.47mmol, 47%) as a yellow solid powder.
Mass spectrometry results of product X: HR-MS (ESI) m/z calcd for C 56 H 24 N 10 836.2185,found 836.2198.
Example 25 preparation of Polymer of formula Y
The specific reaction steps IV-25 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is the same as in the original example 1 Is replaced by a 25 (924.6mg, 3.0mmol, 3.0equiv) to obtain product Y (689.2mg, 0.77mmol, 77%) as a yellow solid powder.
Mass spectrometry analysis of product Y: HR-MS (ESI) m/z calcd for C 64 H 38 N 4 O 2 894.2995,found 894.3014.
Example 26 preparation of Polymer of formula Z
The specific reaction steps IV-26 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 26 (762.4mg, 3.0mmol, 3.0equiv) to give product Z (708.2mg, 0.90mmol, 90%) as a yellow solid powder.
Mass spectrometry results of product Z: HR-MS (ESI) m/z calcd for C 58 H 34 N 4 786.2783,found 786.2795.
Example 27 preparation of Polymer of formula AA
The specific reaction steps IV-27 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is the same as in the original example 1 Is replaced by a 27 (762.4mg, 3.0mmol, 3.0equiv) to obtain a yellow solid powder of product AA (637.4mg, 0.81mmol, 81%).
Mass spectrometry results for product AA: HR-MS (ESI) m/z calcd for C 58 H 34 N 4 786.2783,found 786.2799.
Example 28 preparation of Polymer of formula AB
The specific reaction steps IV-28 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is as in the previous example 1 Is replaced by a 28 (912.6mg, 3.0mmol, 3.0equiv) to obtain product AB as a yellow solid powder (727.4mg, 0.82mmol, 82%).
Mass spectrometry analysis of product AB: HR-MS (ESI) m/z calcd for C 66 H 38 N 4 886.3096,found 886.3108.
Example 29 preparation of Polymer of formula AC
The specific reaction steps IV-29 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is the same as in the original example 1 Is replaced by a 29 (912.6mg, 3.0mmol, 3.0equiv) to obtain a yellow solid powder of product AC (576.6mg, 0.65mmol, 65%).
Mass spectrometry results of product AC: HR-MS (ESI) m/z calcd for C 66 H 38 N 4 886.3096,found 886.3115.
Example 30 preparation of Polymer of formula AD
The specific reaction steps IV-30 are as follows:
this example is essentially the same as the synthesis of compound A, except that a is the same as in the original example 1 Is replaced by a 30 (912.6mg, 3.0mmol, 3.0equiv) to obtain product AD (656.4mg, 0.74mmol, 74%) as a yellow solid powder.
Mass spectrometry results of product AD: HR-MS (ESI) m/z calcd for C 66 H 38 N 4 886.3096,found 886.3099.
Example 31 preparation of Polymer of formula AE
The specific reaction steps IV-31 are as follows:
add Compound C to 100mL schlenk tube 1 (692.4mg, 1.0mmol, 1.0equiv), tris (dibenzylideneacetone) dipalladium (45.8mg, 0.05mmol, 0.05equiv), sodium tert-butoxide (480.5mg, 5.0mmol, 5.0equiv), a 31 (627.9mg, 3.0mmol, 3.0equiv). The reaction mixture was transferred to a glove box and tri-tert-butylphosphine (0.2mL, 0.15equiv,10% in toluene) and dry toluene solvent (30 mL) were added. The screw plug was screwed and removed from the glove box and heated with stirring at 110 ℃ for 12 hours. After the reaction is finished, the solvent is dried by rotary drying under reduced pressure to obtain a crude product. The crude product was passed through a silica gel column (mobile phase petroleum ether: dichloromethane = 5) to give the product AE as a yellow-green solid (873.2mg, 0.92mmol, 92%).
Mass spectrometry results for example AE: HR-MS (ESI) m/z calcd for C 68 H 48 N 6 948.3940,found 948.3955.
Example 32 preparation of Polymer of formula AF
The specific reaction steps IV-32 are as follows:
this example is essentially the same as the synthesis of compound AE except that a is the same as in the original example 31 Change to a 32 (549.6 mg,3.0mmol, 3.0equiv) to obtain a yellowish green solid product AF (798.3mg, 0.89mmol, 89%).
Mass spectrometry results for example AF: HR-MS (ESI) m/z calcd for C 62 H 36 N 6 O 2 896.2900,found 896.2911.
Example 33 preparation of Polymer of formula AG
The specific reaction steps IV-33 are as follows:
this example is essentially the same as the synthesis of compound AE, except that a is the same as in the previous example 31 Change to a 33 (597.8mg, 3.0mmol, 3.0equiv) to obtain a yellowish green solid product AG (780.5mg, 0.84mmol, 84%).
Mass spectrometry results for example AG: HR-MS (ESI) m/z calcd for C 62 H 36 N 6 S 2 928.2443,found 928.2458.
Example 34 preparation of Polymer of formula AH
The specific reaction step V-1 is as follows:
add Compound C to a 100mL two-necked flask 2 (916.8mg,1.0mmol,1.0equiv)，a 1 (612.2mg, 3.0mol, 3.0equiv), tetrakis (triphenylphosphine) palladium (57.8mg, 0.05mmol, 0.05equiv) and potassium carbonate (691mg, 5.0mmol, 5.0equiv) and evacuation of gas three times. Degassed toluene/water (20/5 mL) was added and heated to 100 ℃ for 24 hours. After the reaction is finished, the solvent is dried by rotary drying under reduced pressure to obtain a crude product. The crude product was passed through a silica gel column (mobile phase petroleum ether: dichloromethane = 4)Substance AH (665.2mg, 0.73mmol, 73%).
Mass spectrometry analysis of product AH: HR-MS m/z calcd for C 66 H 62 N 4 910.4974,found 910.4988。
Example 34 preparation of Polymer of formula AH
The specific reaction step V-2 is as follows:
this example is substantially the same as the synthesis of Compound AH, except that a is the same as in the previous example 1 Is replaced by a 2 (1.88g, 3.0mmol, 3.0equiv) to obtain product AI (742.1mg, 0.79mmol, 79%) as a white solid powder.
Mass spectrometry results of product AI: HR-MS (ESI) m/z calcd for C 68 H 66 N 4 938.5287,found 938.5298.
Example 35 preparation of Polymer of formula AJ
The specific reaction step V-3 is as follows:
this example is essentially the same as the synthesis of compound AH, except that a is as in the previous example 1 Is replaced by a 3 (702.3mg, 3.0mmol,3.0 equiv) to give the product AJ (747.9mg, 0.77mmol, 77%) as a white solid.
Mass spectrometry analysis result of product AJ: HR-MS (ESI) m/z calcd for C 68 H 66 N 4 O 2 970.5186,found 970.5197.
Example 35 preparation of Polymer of formula AK
The specific reaction step V-4 is as follows:
this implementationThe example is substantially the same as the synthesis of Compound AH, except that a is the same as in the previous example 1 Is replaced by a 4 (657.3mg, 3.0mmol,3.0 equiv) to give product AK (559.1mg, 0.78mmol, 78%) as a yellow solid powder.
Mass spectrometry analysis result of product AK: HR-MS (ESI) m/z calcd for C 66 H 64 N 6 940.5192,found 940.5203.
Example 35 preparation of Polymer of formula AL
The specific reaction step V-5 is as follows:
this example is essentially the same as the synthesis of compound AH, except that a is as in the previous example 1 Is replaced by a 5 (729.3mg, 3.0mmol, 3.0equiv) to obtain product AL (751.9mg, 0.76mmol, 76%) as a yellow solid powder.
Mass spectrometry results for product E: HR-MS (ESI) m/z calcd for C 70 H 64 N 6 988.5192,found 988.5208.
Example 36 preparation of Polymer of formula AM
The specific reaction step V-6 is as follows:
this example is essentially the same as the synthesis of compound AH, except that a is as in the previous example 1 Is replaced by a 6 (696.3mg, 3.0mmol, 3.0equiv) to obtain product AM (802.8mg, 0.83mmol, 83%) as a yellow solid powder.
Mass spectrometry analysis of product AM: HR-MS (ESI) m/z calcd for C 68 H 62 N 4 O 2 966.4873,found 966.4889.
Example 37 preparation of Polymer of formula AN
The specific reaction step V-7 is as follows:
this example is substantially the same as the synthesis of Compound AH, except that a is the same as in the previous example 1 Is replaced by a 7 (786.3mg, 3.0mmol,3.0 equiv) to give the product AN (883.5mg, 0.65mmol, 86%) as a yellow solid powder.
Mass spectrometry analysis of product AN: HR-MS (ESI) m/z calcd for C 70 H 66 N 4 O 4 1026.5084,found 1026.5097.
Example 38 preparation of a Polymer of the formula AO
The specific reaction step V-8 is as follows:
this example is essentially the same as the synthesis of compound AH, except that a is as in the previous example 1 Is replaced by a 8 (924.6mg, 3.0mmol, 3.0equiv) to obtain the product AO (973.9mg, 0.87mmol, 87%) as a yellow solid powder.
Mass spectrometry results for product AO: HR-MS (ESI) m/z calcd for C 80 H 70 N 4 O 2 1118.5499,found 1118.5513.
Example 39 preparation of a Polymer of formula AP
The specific reaction step V-9 is as follows:
this example is essentially the same as the synthesis of compound AH, except that a is as in the previous example 1 Is replaced by a 9 (654.3mg, 3.0mmol,3.0 equiv) to give product AP (666.9mg, 0.71mmol, 71%) as a yellow solid powder.
Mass spectrometry analysis result of product AP: HR-MS (ESI) m/z calcd for C 68 H 66 N 4 938.5287,found 938.5298.
EXAMPLE 40 preparation of Polymer of formula AQ
The specific reaction step V-10 is as follows:
this example is essentially the same as the synthesis of compound AH, except that a is as in the previous example 1 Is replaced by a 10 (654.3mg, 3.0mmol, 3.0equiv) to obtain the product AQ (666.9mg, 0.71mmol, 71%) as a yellow solid powder.
Mass spectrometry results of product AQ: HR-MS (ESI) m/z calcd for C 68 H 66 N 4 938.5287,found 938.5298.
Example 41 preparation of Polymer of formula AR
This example is essentially the same as the synthesis of compound AH, except that a is as in the previous example 1 Is replaced by a 11 (738.5mg, 3.0mmol, 3.0equiv) to obtain the product AR (487.8mg, 0.49mmol, 49%) as a yellow solid powder.
Mass spectrometry results of product AR: HR-MS (ESI) m/z calcd for C 72 H 74 N 4 994.5913,found 994.5926.
Example 42 preparation of Polymer of formula AS
The specific reaction step V-12 is as follows:
this example is substantially the same as the synthesis of Compound AH, except that a is the same as in the previous example 1 Is replaced by a 12 (702.3mg, 3.0mmol, 3.0equiv) to obtain a yellow solid powder of the product AS (825.6mg, 0.85mmol, 85%).
Mass spectrometry results of product AS: HR-MS (ESI) m/z calcd for C 68 H 66 N 4 O 2 970.5186,found 970.5198.
Example 43 preparation of a Polymer of formula AT
The specific reaction step V-13 is as follows:
this example is substantially the same as the synthesis of Compound AH, except that a is the same as in the previous example 1 Is replaced by a 13 (702.3mg, 3.0mmol,3.0 equiv) to give the product AT (641.1mg, 0.66mmol, 66%) as a yellow solid powder.
Mass spectrometry results of the product AT: HR-MS (ESI) m/z calcd for C 68 H 66 N 4 O 2 970.5186,found 970.5204.
Example 44 preparation of Polymer of formula AU
The specific reaction step V-14 is as follows:
this example is essentially the same as the synthesis of compound AH, except that a is as in the previous example 1 Is replaced by a 14 (792.4mg, 3.0mmol, 3.0equiv) to obtain product AU (752.9mg, 0.73mmol, 73%) as yellow solid powder.
Mass spectrometry results of product AU: HR-MS (ESI) m/z calcd for C 70 H 70 N 4 O 4 1030.5397,found 1030.5411.
Example 45 preparation of a Polymer of formula AV
The specific reaction step V-15 is as follows:
this example is essentially the same as the synthesis of compound AH, except that a is as in the previous example 1 Is replaced bya 15 (882.5mg, 3.0mmol, 3.0equiv) to obtain the product AV (447.5mg, 0.41mmol, 41%) as a yellow solid powder.
Mass spectrometry results of product AV: HR-MS (ESI) m/z calcd for C 72 H 74 N 4 O 6 1090.5608,found 1090.5617.
Example 46 preparation of a Polymer of the formula AW
The specific reaction step V-16 is as follows:
this example is substantially the same as the synthesis of Compound AH, except that a is the same as in the previous example 1 Is replaced by a 16 (657.3mg, 3.0mmol,3.0 equiv) to give the product AW (800.1mg, 0.85mmol, 85%) as a yellow solid powder.
Mass spectrometry results of product AW: HR-MS (ESI) m/z calcd for C 66 H 64 N 6 940.5192,found 940.5207.
Example 47 preparation of Polymer of formula AX
The specific reaction step V-17 is as follows:
this example is substantially the same as the synthesis of Compound AH, except that a is the same as in the previous example 1 Is replaced by a 17 (657.3mg, 3.0mmol, 3.0equiv) to obtain a yellow solid product AX (593.0mg, 0.63mmol, 63%) as a powder.
Mass spectrometry results of product AX: HR-MS (ESI) m/z calcd for C 66 H 64 N 6 940.5192,found 940.5215.
Example 48 preparation of Polymer of formula AY
The specific reaction step V-18 is as follows:
this example is essentially the same as the synthesis of compound AH, except that a is as in the previous example 1 Is replaced by a 18 (687.3mg, 3.0mmol, 3.0equiv) to obtain a product AY (778.6mg, 0.81mmol, 81%) as a yellow solid powder.
Mass spectrometry analysis result of product AY: HR-MS (ESI) m/z calcd for C 68 H 60 N 6 960.4879,found 960.4887.
Example 49 preparation of Polymer of formula AZ
The specific reaction step V-19 is as follows:
this example is essentially the same as the synthesis of compound AH, except that a is as in the previous example 1 Is replaced by a 19 (687.3mg, 3.0mmol,3.0 equiv) to give AZ (596.0 mg,0.62mmol, 62%) as a yellow solid product.
Mass spectrometry results of product AZ: HR-MS (ESI) m/z calcd for C 68 H 60 N 6 960.4879,found 960.4887.
Example 50 preparation of Polymer of formula BA
The specific reaction step V-20 is as follows:
this example is essentially the same as the synthesis of compound AH, except that a is as in the previous example 1 Is replaced by a 20 (762.3mg, 3.0mmol,3.0 equiv) to give the product BA (819.1mg, 0.81mmol, 81%) as a yellow solid powder.
Mass spectrometry result of product BA: HR-MS (ESI) m/z calcd for C 70 H 58 N 8 1010.4784,found 1010.4798.
Example 51 preparation of Polymer of formula BB
The specific reaction step V-21 is as follows:
this example is essentially the same as the synthesis of compound AH, except that a is as in the previous example 1 Is replaced by a 21 (837.3mg, 3.0mmol, 3.0equiv) to obtain a product BB (435.1mg, 0.41mmol, 41%) as a yellow solid powder.
Mass spectrometry analysis of product BB results: HR-MS (ESI) m/z calcd for C 72 H 56 N 10 1060.4689,found 1060.4697.
Example 52 preparation of Polymer of formula BC
The specific reaction step V-22 is as follows:
this example is substantially the same as the synthesis of Compound AH, except that a is the same as in the previous example 1 Is replaced by a 22 (786.3mg, 3.0mmol, 3.0equiv) to obtain the product BC (852.7mg, 0.83mmol, 83%) as a yellow solid powder.
Mass spectrometry results of product BC: HR-MS (ESI) m/z calcd for C 70 H 66 N 4 O 4 1026.5084,found 1026.5097.
Example 53 preparation of Polymer of formula BD
The specific reaction step V-23 is as follows:
this example is substantially the same as the synthesis of Compound AH, except that a is the same as in the previous example 1 Is replaced by a 23 (786.3mg, 3.0mmol, 3.0equiv) to obtain the product BD (688.3mg, 0.67mmol, 67%) as a yellow solid powder.
Mass spectrometry results of product BD: HR-MS (ESI) m/z calcd for C 70 H 66 N 4 O 4 1026.5084,found 1026.5091.
Example 54 preparation of a Polymer of formula BE
The specific reaction step V-24 is as follows:
this example is substantially the same as the synthesis of Compound AH, except that a is the same as in the previous example 1 Is replaced by a 24 (837.3mg, 3.0mmol, 3.0equiv) to obtain a product BE as a yellow solid powder (839.6mg, 0.75mmol, 75%).
Mass spectrometry analysis result of product BE: HR-MS (ESI) m/z calcd for C 80 H 70 N 4 O 2 1118.5499,found 1118.5521.
Example 55 preparation of a Polymer of formula BF
The specific reaction step V-25 is as follows:
this example is substantially the same as the synthesis of Compound AH, except that a is the same as in the previous example 1 Is replaced by a 25 (924.6mg, 3.0mmol, 3.0equiv) to obtain BF (716.5mg, 0.64mmol, 64%) as a yellow solid powder product.
Mass spectrometry analysis of product BF: HR-MS (ESI) m/z calcd for C 80 H 70 N 4 O 2 1118.5499,found 1118.5527.
Example 56 preparation of Polymer of formula BG
The specific reaction step V-26 is as follows:
this example is essentially the same as the synthesis of compound AH, except that a is as in the previous example 1 Is replaced by a 26 (762.4mg, 3.0mmol, 3.0equiv) to obtain a yellow solid powder of product BG (890.0mg, 0.88mmol, 88%).
Mass spectrometry results of product BG: HR-MS (ESI) m/z calcd for C 74 H 66 N 4 1010.5287,found 1010.5298.
Example 57 preparation of Polymer of formula BH
The specific reaction step V-27 is as follows:
this example is essentially the same as the synthesis of compound AH, except that a is as in the previous example 1 Is replaced by a 27 (762.4mg, 3.0mmol, 3.0equiv) to give product BH (738.3mg, 0.73mmol, 73%) as a yellow solid powder.
Mass spectrometry analysis of product BH: HR-MS (ESI) m/z calcd for C 74 H 66 N 4 1010.5287,found 1010.5293.
Example 58 preparation of the Polymer of formula BI
The specific reaction step V-28 is as follows:
this example is substantially the same as the synthesis of Compound AH, except that a is the same as in the previous example 1 Is replaced by a 28 (912.6 mg,3.0mmol,3.0 equiv) to give product BI as a yellow solid (789.2mg, 0.71mmol, 71%).
Mass spectrometry results of product BI: HR-MS (ESI) m/z calcd for C 82 H 70 N 4 1110.5600,found 1110.5624.
Example 59 preparation of Polymer of formula BJ
The specific reaction step V-29 is as follows:
this example is substantially the same as the synthesis of Compound AH, except that a is the same as in the previous example 1 Is replaced by a 29 (912.6mg, 3.0mmol, 3.0equiv) to obtain a yellow solid powder product BJ (622.4mg, 0.56mmol, 56%).
Mass spectrometry analysis of product BJ results: HR-MS (ESI) m/z calcd for C 82 H 70 N 4 1110.5600,found 1110.5619.
Example 60 preparation of a Polymer of formula BK
The specific reaction step V-30 is as follows:
this example is substantially the same as the synthesis of Compound AH, except that a is the same as in the previous example 1 Is replaced by a 30 (912.6mg, 3.0mmol, 3.0equiv) to obtain a product BK (477.9mg, 0.43mmol, 43%) as a yellow solid powder.
Mass spectrometry of the product BK: HR-MS (ESI) m/z calcd for C 82 H 70 N 4 1110.5600,found 1110.5611.
Example 61 preparation of Polymer of formula BL
The specific reaction step V-31 is as follows:
add Compound C to 100mL schlenk tube 2 (916.8mg, 1.0mmol, 1.0equiv), tris (dibenzylideneacetone) dipalladium (45.8mg, 0.05mmol, 0.05equiv), sodium tert-butoxide (480.5mg, 5.0mmol, 5.0equiv), a 31 (627.9mg, 3.0mmol, 3.0equiv). The reaction mixture was transferred to a glove box and tri-tert-butylphosphine (0.2mL, 0.15equiv,10% in toluene) and dry toluene solvent (30 mL) were added. The screw stopper was screwed and removed from the glove box and heated with stirring at 110 ℃ for 12 hours. After the reaction is finished, the solvent is dried by rotary drying under reduced pressure to obtain a crude product. The crude product is passed through a silica gel column (mobile phase is petroleum ether: dichloromethane = 6)To product BL as a yellow-green solid (1032.8mg, 0.88mmol, 88%).
Mass spectrometry results for example BL: HR-MS (ESI) m/z calcd for C 84 H 80 N 6 1172.6444,found 1172.6453.
Example 62 preparation of a Polymer of the formula BM
The specific reaction step V-32 is as follows:
this example is essentially the same as the synthesis of compound BM except that a is the same as in the previous example 31 Is changed into a 32 (549.6mg, 3.0mmol, 3.0equiv) to obtain a yellowish green solid product BM (908.4mg, 0.81mmol, 81%).
Mass spectrometry results of example BM: HR-MS (ESI) m/z calcd for C 78 H 68 N 6 O 2 1120.5404,found 1120.5419.
Examples A-BM prepared according to the invention are dissolved in chromatographically pure toluene to give a concentration of 10 -5 Diluted solutions of mol/L, and the photophysical properties of each diluted solution were tested. The maximum absorption wavelength, maximum emission wavelength, phosphorescence lifetime and long afterglow duration in liquid nitrogen are shown in table 1. The phosphorescence lifetime decay curve and the long afterglow picture demonstration of the compound E in liquid nitrogen are shown in figure 1. As can be seen from the results of Table 1 and FIG. 1, the series of aromatic hydrocarbon derivatives based on the biphenyl structure all exhibited long phosphorescence lifetime (1.44 to 3.29 s) and long afterglow time (18 to 40 s) at low temperature.
TABLE 1 photophysical Properties of Compounds A-BM
The invention obtains a series of micromolecules with low-temperature long afterglow property through C-C coupling and C-N coupling reaction. Under the condition of extremely low temperature environment (liquid nitrogen), the special organic small molecules can emit extremely strong phosphorescence with extremely long service life by photoinduced excitation. After the excitation light source is turned off, the light can continuously emit for 18-40 s. The material shows a fast intersystem crossing rate and a slow phosphorescent radiation transition rate through analysis on a photophysical process, wherein the faster the intersystem crossing rate is, the slower the phosphorescent radiation transition rate is, and the longer the afterglow phenomenon is shown at a low temperature. Based on the special property, the material has a plurality of potential applications in extremely low temperature environment, such as optical encryption, biological imaging and the like.
Claims (10)
1. A low-temperature ultra-long afterglow molecular material has a structural formula shown as formula TM;
in formula TM, the group donor is an electron-rich donor group selected from carbazole and 3, 6-di-tert-butylcarbazole.
The group X is any one of benzene ring, substituted benzene ring, naphthalene ring, perylene ring, pyrene ring, carbazole, 3, 6-di-tert-butyl carbazole, 9, 10-dihydroacridine, phenoxazine and phenothiazine.
2. The low-temperature ultra-long afterglow molecular material of claim 1, which is characterized in that: the substituted benzene ring is any one of a 2-substituted benzene ring, a 3-substituted benzene ring, a 4-substituted benzene ring, a 3, 5-disubstituted benzene ring and a 2,4, 6-trisubstituted benzene ring, wherein the substituent is selected from methyl, methoxy, amino, cyano, aldehyde group, ester group and phenylcarbonyl.
3. The low-temperature ultra-long afterglow molecular material of claim 1 or 2, which is characterized in that: the group X is selected from the formula a 1 ～a 33 Any of the structures shown;
4. the preparation method of the low-temperature ultra-long afterglow molecular material of any one of claims 1-3, comprising the following steps:
1) Formula A 1 Amidating and dehydrating the compound with sulfamide to obtain the formula B 1 A compound shown in the specification;
2) In the presence of sodium hydride, formula B 1 Nucleophilic substitution reaction is carried out on the compound and a compound corresponding to electron donating group donor to respectively obtain a compound shown as a formula C 1 A compound of formula C 2 A compound shown in the specification;
the electron-donating group donor is an electron-rich donor group and is selected from carbazole and 3, 6-di-tert-butyl carbazole;
3) Formula C 1 A compound shown as or C 2 The compound and a compound corresponding to the group X are subjected to Suzuki coupling reaction or Buchwald-Hartwig coupling reaction to obtain the low-temperature ultra-long afterglow molecular material shown in the formula TM;
the radical X is as defined for formula TM.
5. The method of claim 4, wherein: in step 1), the amidation reaction and the dehydration reaction are carried out in sulfolane;
formula A 1 The molar ratio of the compound to the sulfonamide is 1:2 to 4;
the reaction proceeds as follows: reacting for 3-4 hours at 160 ℃;
no inert gas is required for protection.
6. The production method according to claim 4 or 5, characterized in that: in step 2), the nuclear substitution reaction comprises the following steps:
will be represented by the formula B 1 Stirring the compound and the sodium hydride in dry N, N-dimethylformamide at room temperature for 0.5 to 1 hour, then adding a compound corresponding to the group donor, and reacting at 60 to 80 ℃ for 10 to 12 hours;
formula B 1 The molar ratio of the compound, the sodium hydride and the compound corresponding to the group donor is 1: 1.1-1.2: 1.9 to 2.
An inert gas blanket is required.
7. The production method according to any one of claims 4 to 6, 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;
formula C 1 A compound of the formula C 2 The molar ratio of the compound, the compound corresponding to the group X, the tetrakis (triphenylphosphine) palladium and the potassium carbonate is 1:1 to 1.05: 0.05-0.1: 5 to 8 percent;
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 h;
an inert gas blanket is required.
8. The production method according to any one of claims 4 to 7, characterized in that: in the step 3), the Buchwald-Hartwig coupling reaction conditions are as follows:
in the presence of tris (dibenzylideneacetone) dipalladium and sodium tert-butoxide;
formula C 1 A compound of the formula C 2 The molar ratio of the compound, the compound corresponding to the group X, the tris (dibenzylideneacetone) dipalladium and the sodium tert-butoxide is 1:1 to 1.05:0.05 to 0.1:5 to 8 percent;
the solvent is dry toluene;
the reaction temperature is 105-110 ℃;
the reaction time is 20-24 h;
an inert gas blanket is required.
9. The use of the low-temperature ultra-long afterglow molecular material of any one of claims 1 to 3 as or in the preparation of organic luminescent materials.
10. The application of the low-temperature ultra-long afterglow molecular material of any one of claims 1 to 3 in anti-counterfeiting encryption, biological imaging and optical temperature probes.
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| CN105418486A (en) * | 2015-12-25 | 2016-03-23 | 上海天马有机发光显示技术有限公司 | Organic electroluminescent compound and organic photoelectric device thereof |
| US20180215711A1 (en) * | 2015-05-06 | 2018-08-02 | Samsung Sdi Co., Ltd. | Dopant for organic optoelectronic device, organic optoelectronic device and display device |
| 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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| US20180215711A1 (en) * | 2015-05-06 | 2018-08-02 | Samsung Sdi Co., Ltd. | Dopant for organic optoelectronic device, organic optoelectronic device and display device |
| CN105418486A (en) * | 2015-12-25 | 2016-03-23 | 上海天马有机发光显示技术有限公司 | Organic electroluminescent compound and organic photoelectric device thereof |
| 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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