A conjugated microporous carbazole polymer, its preparation method and application, and a fluorescent film and its preparation method
A technology of conjugated micropores and polymers, used in fluorescence/phosphorescence, material analysis by optical means, instruments, etc., to achieve the effects of good stability, high selectivity, and strong fluorescence quenching effect
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[0046] The present invention provides a method for preparing a conjugated microporous carbazole polymer described in the above scheme, comprising the following steps:
[0047] Under the action of an oxidizing agent, 1,3,6,8-tetrakis(4-(9H-carbazol-9-yl)phenylpyrene (L) is oxidatively polymerized in an organic solvent to obtain a compound having the structure shown in formula I The conjugated microporous carbazole polymer (referred to as CK-CMP).
[0048] In the present invention, the equation of the oxidative polymerization reaction is shown in formula II:
[0049]
[0050] In the present invention, the 1,3,6,8-tetrakis(4-(9H-carbazol-9-yl)phenylpyrene is preferably prepared by the following steps:
[0051] Suizik coupling reaction of 1,3,6,8-tetrabromopyrene, 4-(9H-carbazol-9-yl)phenylboronic acid, basic substance and palladium catalyst in a solvent gives 1,3,6, 8-Tetrakis(4-(9H-carbazol-9-yl)phenylpyrene.
[0052] In the present invention, the alkaline substance prefer...
Embodiment 1
[0088] (1) Preparation of 1,3,6,8-tetrakis(4-(9H-carbazol-9-yl)phenylpyrene (L)
[0089] Add 1,3,6,8-tetrabromopyrene (1.0356g, 2mmol), 4-(9H-carbazol-9-yl)phenylboronic acid (2.8712g, 10mmol) and potassium carbonate in a 250mL three-neck round bottom flask (3.15g, 23mmol), Pd(PPh 3 ) 4 (0.6g, 0.50mmol), dioxane 100mL and 10mL distilled water, this system is in N 2 The reaction was stirred at 100°C for 3 days in the atmosphere. After the reaction, the yellow reaction mixture was cooled to room temperature, transferred to dilute hydrochloric acid solution (100 mL), filtered and washed with water (3×40 mL). After the filter cake was dried, it was washed with CHCl 2 Carry out Soxhlet extraction for 48h, CHCl 2 The extract was evaporated under reduced pressure, and the obtained crude product L was further purified by silica gel column chromatography to obtain 0.5 g of a bright yellow solid (yield 22%)
[0090] The proton spectrum data of gained product is:
[0091] 1HNMR (4...
Embodiment 2
[0137] Other conditions are consistent with Example 1, only the consumption of monomer L in step (2) is changed to 0.6mmol, the oxidizing agent is changed to ammonium persulfate, and polymer CK-CMP, CK-CMP suspension, and CK-CMP are prepared respectively. CMP fluorescent film.
[0138] Physical characterization and fluorescent performance tests were performed on CK-CMP, CK-CMP suspension and CK-CMP fluorescent film according to the above method, and the test results were similar to those in Example 1.
[0139] According to the above examples, it can be seen that the present invention successfully synthesized the oxidative self-polymerization of 1,3,6,8-tetrakis(4-(9H-carbazol-9-yl)phenyl)pyrene (L) by oxidizing agent The conjugated microporous carbazole polymer as the core, especially the introduction of pyrene in the three-dimensional framework, makes the polymer exhibit strong luminescent properties in various polar solvents under ultraviolet light irradiation; and the polym...
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