One-Step Synthesis of Ladder-Type Fused Poly(benzopentalene) Derivatives with Tunable Energy Levels by Variable Substituents

Novel ladder-type conjugated polymers, fused poly (benzopentalene) derivatives, were synthesized from the readily accessible 1,4-dibromo-2,5-diethynylbenzene derivatives by the Pd-catalyzed self-polycondensation in one-step with high yields. The low solubility of the ladder structure was suggested when the triisopropylsilyl substituents were selected. However, when longer alkyl chains were introduced into the peripheral moieties, such as the dialkylanilino (DAA) and alkyloxyphenyl groups, a high solubility was achieved and the number-average molecular weight (M-n) reached 18,000. The UV-Vis absorption spectral shapes of the polymers were similar to the reported dibenzopentalene derivatives, except for the bathochromically shifted end absorptions. This result suggests an extension of the pi-conjugated systems due to the polymerization. Moreover, the almost defect-free structure of the ladder-type polymers was confirmed by the quantitative tetracyanoethylene (TCNE) addition to the DAA-activated alkynes. The titration experiments of TCNE to the polymers revealed the number of terminal alkynes, which enabled us to calculate the molecular weight of the polymers. The calculated molecular weight was consistent with that determined by GPC. After the TCNE addition, the polymer band gaps reasonably decreased as suggested by the UV-Vis-NIR absorption and electrochemical measurements. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 72-81, 2011