Synthesis and Characterization of Conjugated Polymers Containing Bifluorenylidenes Units†

doi:10.7503/cjcu20130969

Abstract

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

CLC Number:

O631

TrendMD:

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

Figures/Tables 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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