Diradical Character Based Design for Singlet Fission of Bisanthene Derivatives: Aromatic-Ring Attachment and π-Plane Twisting
Diradical Character Based Design for Singlet Fission of Bisanthene Derivatives: Aromatic-Ring Attachment and π-Plane Twisting
复制标题
基于双自由基特征的双蒽衍生物单线态裂变设计：芳香环连接和 π 平面扭曲
DOI：
10.1021/acs.jpclett.6b01885
复制
发表时间：
2016
影响因子：
4.4
通讯作者：
M. Nakano
中科院分区：
文献类型：
--
作者：
S. Ito;T. Nagami;M. Nakano
我们展示了一个基于双自由基特征的多环芳烃，双蒽衍生物的单线态裂变的分子设计。为了满足单重态裂变的能级匹配条件，本文研究了芳香环连接和π平面扭曲两种化学修饰。利用非核依赖化学位移、分子轨道及其能量对模型分子的电子结构进行了详细的分析，证明了共振结构与芳香性之间的关系以及π共轭体系的非平面性与轨道重叠减少之间的关系对于调节双自由基性质的有用性。这一结果提供了一个新的多环芳烃的设计准则，朝着有效的单线态裂变。
We demonstrate a diradical character-based molecular design for singlet fission using polycyclic aromatic hydrocarbons, bisanthene derivatives. Two types of chemical modificationsaromatic-ring attachment and π-plane twistingare examined in order to satisfy the energy level matching condition for singlet fission. Detailed analysis of the electronic structures of the model molecules using nucleus-independent chemical shift, molecular orbitals, and their energies has demonstrated the usefulness of the relationship between the resonance structure and aromaticity and that between nonplanarity of π-conjugated systems and reduction of orbital overlap for tuning the diradical character. This result provides a novel design guideline for polycyclic aromatic hydrocarbons toward efficient singlet fission.