Novel dibenzo[a, e] pentalene-based conjugated polymers
Novel dibenzo[a, e] pentalene-based conjugated polymers
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DOI：
10.1039/c3tc31630k
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发表时间：
2014-01-01
影响因子：
6.4
通讯作者：
Koganezawa, Tomoyuki
中科院分区：
文献类型：
--
作者：
Nakano, Masahiro;Osaka, Itaru;Koganezawa, Tomoyuki
二苯并[a，e]并环戊二烯（DBP）是一种具有16 π反芳环性质的梯形稠环体系，通过低聚噻吩结构单元将其引入共轭聚合物中，考察DBP作为半导体聚合物结构单元的潜力.根据DBP单元在聚合物主链中的掺入方式，通过5，10-或2，7-位置，聚合物显示出不同的颜色，反映了不同的电子结构，尽管从循环伏安图估计的HOMO和LUMO能级几乎相同。有趣的是，在其场效应晶体管（FET）的特性中观察到掺入方式的影响。对于PDTDBP 2 T，其中DBP单元通过5，10-位整合到聚合物主链中，DBP单元表现得像“二苯并成环的1，3-丁二烯”部分，并且它们的FET特性受到取向有序和结晶度的强烈影响，类似于普通的“仅供体”聚合物，如P3 HT。另一方面，iPDTDBP 2 Ts，其中整个16 p DBP单元通过2，7-位整合到聚合物主链中，表现得像某种供体-受体聚合物，并且FET特性与取向顺序无关：场效应迁移率高于0.1 cm（2）V-1 s（-1），而与薄膜中的聚合物取向无关。从这些结果中，我们可以认识到16 π反芳香族DBP单元作为一个有用的结构单元，具有可转化的性质，用于开发新的共轭聚合物。
Dibenzo[a, e] pentalene (DBP), a ladder-type fused-ring system with 16 pi anti-aromatic nature, is integrated into conjugated polymers with oligothiophene building blocks to examine the potential of DBP as a new building block for semiconducting polymers. Depending on the incorporation manner of the DBP unit in the polymer backbone, via the 5,10- or 2,7-positions, the polymers show distinct colours, reflecting the different electronic structures, though the HOMO and LUMO energy levels estimated from cyclic voltammograms are almost the same. Interestingly, the impact of the incorporation manner was observed in the characteristics of their field-effect transistors (FETs). For PDTDBP2Ts, in which the DBP units are integrated into the polymer backbone via the 5,10- positions, the DBP units behave like a "dibenzo-annulated 1,3-butadiene" moiety, and their FET characteristics are strongly affected by orientational ordering and crystallinity, similar to ordinary "donor-only" polymers such as P3HT. On the other hand, iPDTDBP2Ts, in which the whole 16p DBP unit is integrated into the polymer backbone via the 2,7-positions, behave like a certain kind of donor-acceptor polymers, and the FET characteristics are independent of orientational order: the field-effect mobilities are higher than 0.1 cm(2) V-1 s(-1) regardless of the polymer orientation in the thin film. From these results, we can recognize the 16 pi anti-aromatic DBP unit as a useful building block with transmutable nature for the development of new conjugated polymers.