Poly(iminoborane)s: An Elusive Class of Main-Group Polymers?
Poly(iminoborane)s: An Elusive Class of Main-Group Polymers?
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DOI：
10.1002/anie.201607131
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发表时间：
2016-10-10
影响因子：
16.6
通讯作者：
Helten, Holger
中科院分区：
文献类型：
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作者：
Ayhan, Ozan;Eckert, Thomas;Helten, Holger
聚硅氧烷(有机硅)的商业相关性最清楚地证明了无机主基聚合物的重要性。基于有机硼的材料，如p-共轭有机硼烷聚合物和BN掺杂的多环芳烃，目前正引起人们的极大关注。令人惊讶的是，聚(亚胺硼烷)S(PIB；[BRNR‘](N))，即母体不饱和BN聚合物，在形式上与聚乙炔是等电子的，到目前为止还没有令人信服的表征。在这里，我们介绍了一种平均由12-14个BN单元组成的直链低聚(亚胺硼烷)的合成和综合表征。使用我们的合成方法，可以有效地抑制不需要的副反应，这些副反应会导致硼氮酮的形成。支持DFT和TD-DFT计算可以更深入地了解齐聚物的微观结构和电子结构。
The significance of inorganic main-group polymers is demonstrated most clearly by the commercial relevance of polysiloxanes (silicones). Organoboron-based materials such as p-conjugated organoborane polymers and BN-doped polycyclic aromatic hydrocarbons are currently attracting considerable attention. Surprisingly, poly(iminoborane)s (PIBs; [BRNR'](n)), that is, the parent unsaturated BN polymers, which are formally isoelectronic to polyacetylene, have not been convincingly characterized thus far. Herein, we present the synthesis and comprehensive characterization of a linear oligo(iminoborane), which comprises a chain of 12-14 BN units on average. With our synthetic approach, unwanted side reactions that result in borazine formation are effectively suppressed. Supporting DFT and TD-DFT calculations provide deeper insight into the microstructure and the electronic structure of the oligomer.