Effect of the conjugation pathway on the electronic structures of p-π* conjugated polymers with fused borepin units
Effect of the conjugation pathway on the electronic structures of p-π* conjugated polymers with fused borepin units
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DOI：
10.1039/d1py00528f
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发表时间：
2021-05-21
影响因子：
4.6
通讯作者：
Ohshita, Joji
中科院分区：
文献类型：
--
作者：
Adachi, Yohei;Arai, Fuka;Ohshita, Joji
在共轭材料中，p-pi*共轭聚合物由于其独特的电子结构而备受关注，这些结构是由硼上的空p轨道与相邻pi系统的pi*轨道之间的轨道相互作用产生的。另一方面，作为含杂原子的芳香族体系，研究了溴甲素（tropylium离子的等电子环体系）。在这项工作中，首次制备了由具有不同共轭途径的四环borepin结构组成的p-pi*共轭聚合物。光学研究表明，与传统的p-pi*共轭聚合物相比，borepin聚合物具有更多的扩展共轭。此外，当溶液中加入氰化物时，两种borepin聚合物表现出截然不同的光学响应。光物理测量和DFT计算揭示了borepin结构的特征电子效应和不同共轭途径的影响。
Among conjugated materials, p-pi* conjugated polymers have attracted much attention due to their unique electronic structures derived from the orbital interaction between the empty p-orbital on boron and the pi*-orbitals of the adjacent pi-systems. On the other hand, borepin, an isoelectronic ring system of tropylium ions, has been investigated as an aromatic system containing heteroatoms. In this work, the first examples of p-pi* conjugated polymers consisting of tetracyclic borepin structures with different conjugation pathways were prepared. Optical investigations revealed that the borepin polymers have more extended conjugations than conventional p-pi* conjugated polymers. Furthermore, the two borepin polymers exhibited drastically different optical responses when cyanide was added to the solution. Photophysical measurements and DFT calculations disclosed the characteristic electronic effects of the borepin structures and the influence of different conjugation pathways.