Anomalous Electronic Properties of Iodous Materials: Application to High-Spin Reactive Intermediates and Conjugated Polymers
Anomalous Electronic Properties of Iodous Materials: Application to High-Spin Reactive Intermediates and Conjugated Polymers
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含碘材料的反常电子性质：在高自旋反应中间体和共轭聚合物中的应用
DOI：
10.1021/acs.joc.9b03289
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Winter, Arthur H.
中科院分区：
文献类型：
--
作者：
Qiu, Yunfan;Winter, Arthur H.
控制带有取代基的芳香族分子的前线轨道能是各种化学和材料应用的关键。在这里，我们研究了一种简单的策略，通过简单地将碘原子放置在彼此相邻的位置来实现芳烃的高能面内轨道。碘分子上的孤对轨道混合在一起，形成高能平面σ-反键轨道作为最高占据分子轨道(HOMO)。我们发现，这种效应可以用来控制轨道间隙、最高占据轨道的对称性以及反应中间体的电子态。这种电子效应并不局限于活性中间体，我们证明了这种碘支撑策略也可以用于在有机电子材料中实现较小的HOMO-最低未占据分子轨道(HOMO-LUMO)能隙。几种最流行的导电聚合物的碘化齐聚物的计算结果表明，与未取代材料相比，其HOMO-LUMO间隙更小。这种用于产生高能面内HOO的碘支撑方法预计将非常普遍。虽然氟材料的不同寻常的性质已经得到了很好的证实，但在元素周期表的另一个极端，碘材料的新性质可能有待发现。
Manipulating frontier orbital energies of aromatic molecules with substituents is key to a variety of chemical and material applications. Here, we investigate a simple strategy for achieving high-energy in-plane orbitals for aromatics simply by positioning iodine atoms next to each other. The lone pair orbitals on the iodines mix to give a high-energy in-plane σ-antibonding orbital as the highest occupied molecular orbital (HOMO). We show that this effect can be used to manipulate orbital gaps, the symmetry of the highest occupied orbital, and the adopted electronic state for reactive intermediates. This electronic effect is not limited to reactive intermediates, and we demonstrate that this iodine buttressing strategy also can be used to achieve small HOMO–lowest unoccupied molecular orbital (HOMO–LUMO) gaps in organic electronic materials. Iodinated oligomers of several of the most popular conducting polymers are computed to have smaller HOMO–LUMO gaps than the unsubstituted materials. This iodine buttressing approach for generating high-energy in-plane HOMOs is anticipated to be highly general. While the unusual properties of fluorous materials are well established, at the other extreme on the periodic table novel properties of iodous materials may await discovery.