B-N Lewis pair-fused dipyridylfluorene copolymers incorporating electron-deficient benzothiadiazole comonomers
B-N Lewis pair-fused dipyridylfluorene copolymers incorporating electron-deficient benzothiadiazole comonomers
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掺入缺电子苯并噻二唑共聚单体的 B-N Lewis 对稠合二吡啶基芴共聚物
DOI：
10.1038/s41428-022-00723-y
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发表时间：
2023
期刊：
影响因子：
2.8
通讯作者：
Jäkle, Frieder
中科院分区：
文献类型：
--
作者：
Alahmadi, Abdullah F.;Zuo, Jingyao;Jäkle, Frieder
用B-N单元等排取代C-C是一种调节有机π共轭材料光电性能的有效方法。本文采用Stille型缩聚反应制备了B-N刘易斯对稠合二吡啶基芴单体与噻吩基苯并噻二唑（BTDDT）的共聚物。硼上含有环外乙基或五氟苯基取代基的聚合物的特征在于通过多核NMR光谱和凝胶渗透色谱法，其提供30（R = Et）和10（R = C6 F5）的平均聚合度（DPn）的估计。薄膜上的电化学分析揭示了两个不同的可逆还原，被分配到苯并噻二唑和硼稠合的dipyridylfluorene为中心的过程。紫外可见维斯分析表明，相对于BTDDT和含硼单体，带隙显着降低。结果，吸收和发射带被移动到低得多的能量，导致强烈的橙子发射，其最大值分别在641 nm（R = Et）和627 nm（R = C6 F5），量子产率超过50%。通过对分子模型二联体的计算研究，揭示了B-N刘易斯对等排取代梯形稠合双芴中的C-C单元对聚合物电子结构的影响.
The isosteric replacement of C-C with B-N units is emerging as a powerful method to tune the optoelectronic properties of organic π-conjugated materials. In this work, copolymers based on ladder-type B-N Lewis pair-fused dipyridylfluorene monomers and a thienylated benzothiadiazole (BTDDT) are prepared by Stille-type polycondensation. The polymers containing exocyclic ethyl or pentafluorophenyl substituents on boron are characterized by multinuclear NMR spectroscopy and gel permeation chromatography, which provides estimates of the average degrees of polymerization (DPn) of 30 (R = Et) and 10 (R = C6F5). Electrochemical analyses on thin films reveal two distinct reversible reductions that are assigned to benzothiadiazole- and boron-fused dipyridylfluorene-centered processes. UV‒vis analyses show that the band gaps are significantly lowered relative to both BTDDT and the boron-containing monomers. As a result, the absorption and emission bands are shifted to much lower energies, leading to intense orange emission with maxima at 641 nm (R = Et) and 627 nm (R = C6F5), respectively, with quantum yields of over 50%. Computational studies on molecular model dyads offer insights into the effects of the isosteric replacement of C-C units in ladder-type fused bisfluorene with B-N Lewis pairs on the electronic structures of the polymers.
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