含联芴烯单元共轭聚合物的合成及表征

doi:10.7503/cjcu20130969

摘要/Abstract

摘要：

以六羰基钨[W(CO)₆]为催化剂, 合成了聚吲哚芴(P1)、聚梯型四苯(P2)、聚梯型五苯(P3)和小分子9-联吲哚芴烯(S1).该类聚合物的重复单元含有联芴烯结构, 通过芴9位的双键连接. 光学和电化学等实验结果表明, 聚合物无荧光发射, 是一类窄带隙的共轭聚合物, 其中聚合物P1薄膜的紫外吸收值最大波长为710 nm.

关键词: 六羰基钨, 共轭聚合物, 窄带隙, 联芴烯

Abstract:

A series of novel conjugated polymers containing bifluorenylidenes units was synthesized under mild conditions with W(CO)₆ as the catalyst, and the repeated units of the polymers were linked at 9 position of fluorine by the double bond. The new polymers represent narrow band gap, and the maxium absorption of polymer P1 in film is peaked at 710 nm. In most cases, the conjugated polymers containing fluorenes units show strong photoluminescence(PL) emission, while the synthesized polymers show no photoluminescence(PL) emission. The synthesized polymers contain new backbone structure. Their optical and electrochemical properties were studied in detail.

Key words: Tungsten carbonyl[W(CO)6], Conjugated polymer, Low band gap, Bifluorenyidene

中图分类号:

O631

TrendMD:

谭淑贞, 马海霞, 刘薇, 赵洪池, 武永刚, 巴信武. 含联芴烯单元共轭聚合物的合成及表征. 高等学校化学学报, 2014, 35(6): 1355.

TAN Shuzhen, MA Haixia, LIU Wei, ZHAO Hongchi, WU Yonggang, BA Xinwu. Synthesis and Characterization of Conjugated Polymers Containing Bifluorenylidenes Units^†. Chem. J. Chinese Universities, 2014, 35(6): 1355.

图/表 8

Scheme 1 Synthesis of monomers 3,9-di-tert-butyl-5,12-di[(1,3-dithiolane-2-spiro-]indenofluorene(M1) and 6,6'-dioctyl-12,15-[(1,3-dithiolane)-2-spiro-]ladder-typer tetraphenylenes(M2)

Scheme 2 Synthesis of monomers 5,5'-dioctyl-12-[(1,3-dithiolane)-2-spiro-]indenofluorene(M-S1) and 5,14-di-[(1,3-dithiolane)-2-spiro-]-8,17-di-[(3,6-dioctyloxy)fluorene-9-spiro]ladder-type pentaphenylenes(M3)

Scheme 3 Synthesis of polymers poly(indenofluorene)(P1) and poly(ladder-type tetraphenylenes)(P2)

Scheme 4 Synthesis of compound 9-biindenofluorenylidene(S1) and poly(ladder-type pentaphenylenes)(P3)

Fig.1 GPC elution(A) and TGA traces(B) of polymers P1(a), P2(b), P3(c) and compound S1(d) GPC flow rate: 1 mL/min; TGA heating rate: 20 ℃/min.

Fig.2 UV-Vis absorption spectra of polymers P1(A), P2(B), P3(C) and compound S1(D) in CH2Cl2 solution(a) and film(b) (A) [P1]=9.5×10-7 mol/L; (B) [P2]=6.0×10-7 mol/L; (C) [P3]=1.2×10-6 mol/L; (D) [S1]=1.0×10-5 mol/L.

Fig.3 Cyclic voltammograms of polymers P1(A), P2(B), P3(C) and compound S1(D) in CH2Cl2 at a scan rate of 30 mV/s

Table 1 HOMO and LUMO energies and band gap data of polymers P1, P2, P3 and compound S1

Compound	HOMO/eV	LUMO/eV	Band gap/eV
P1	-5.44	-3.59	1.85
P2	-5.56	-2.79	2.77
P3	-5.50	-2.95	2.55
S1	-5.65	-3.02	2.63

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