碘材料的异常电子性能：在高旋转活性中间体和共轭聚合物中的应用。,The Journal of Organic Chemistry

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碘材料的异常电子性能：在高旋转活性中间体和共轭聚合物中的应用。
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-03-01 , DOI: 10.1021/acs.joc.9b03289
Yunfan Qiu ₁ , Arthur H Winter ₁

Affiliation

用取代基操纵芳族分子的前沿轨道能是多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，只需将碘原子彼此相邻放置即可实现芳烃的高能面内轨道。碘上的孤对轨道混合在一起，产生了一个高能平面内σ反键轨道，作为最高占据分子轨道（HOMO）。我们表明，该效应可用于操纵轨道间隙，最高占据轨道的对称性以及反应性中间体采用的电子态。这种电子效应不仅限于反应性中间体，而且我们证明了这种碘支持策略还可以用于实现有机电子材料中较小的HOMO最低空位分子轨道（HOMO-LUMO）间隙。几种最流行的导电聚合物的碘化低聚物经计算比未取代的材料具有更小的HOMO-LUMO间隙。预期这种用于产生高能面内HOMO的碘支持方法是非常普遍的。尽管已经很好地确定了氟材料的非同寻常的特性，但在元素周期表的另一个极端，碘材料的新特性可能有待发现。

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Anomalous Electronic Properties of Iodous Materials: Application to High-Spin Reactive Intermediates and Conjugated Polymers.

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.

更新日期：2020-03-02

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