A Computational Physical Organic Study of a Torque, Lock, and Propagate Approach and Validation with the Synthesis of Configurationally Stable First‐Generation Helically Twisted Acenes
A Computational Physical Organic Study of a Torque, Lock, and Propagate Approach and Validation with the Synthesis of Configurationally Stable First‐Generation Helically Twisted Acenes
复制标题
扭矩、锁定和传播方法的计算物理有机研究以及构型稳定的第一代螺旋扭曲并苯合成的验证
DOI：
10.1002/ejoc.202101533
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发表时间：
2022
影响因子：
2.8
通讯作者：
Arulsamy, Navamoney
中科院分区：
文献类型：
--
作者：
Weber, Jacob A.;Clennan, Edward L.;Arulsamy, Navamoney
由螺旋烯和并苯域组成的杂化多环芳烃（PAH），称为[7]heli-D-并苯，被引入作为支架，通过扭矩、锁定和传播（TLP）方法生成对映体纯扭曲并苯（heli-twistacenes）。使用带有或不带有色散校正的计算方法来探索这些多环芳烃的结构和电子特征，并探索可能使反应混合物复杂化的扭转异构体的可能形成。 [7]heli-D-并苯系列的未取代和二取代成员的合成证实了 TLP 方法的可行性，并与计算结果一起，为这种新方法作为生成对映体纯扭曲并苯的可行方法提供了概念验证。这些第一代螺旋并苯的X射线结构、吸收、荧光、磷光和CD光谱与并五苯和[7]螺旋烯的结构和光物理性质进行了比较。 19,24-二氰基[7]heli-D-蒽的对映体富集的M对映体的高势垒验证了其在室温下的构型稳定性。
Hybrid polyaromatic hydrocarbons (PAHs) consisting of helicene and acene domains, referred to as [7]heli‐D‐acenes, are introduced as scaffolds to generate enantiopure twisted acenes (heli‐twistacenes) by a torque, lock, and propagate (TLP) approach. Computational methods with and without dispersion corrections were used to explore the structural and electronic features of these PAHs and to explore the possible formation of twistomers that might complicate reaction mixtures. Syntheses of unsubstituted and disubstituted members of the [7]heli‐D‐acene series confirmed the viability of the TLP approach, and together with the computational results, provided proof‐of‐concept of this new approach as a viable means to generate enantiopure twisted‐acenes. The X‐ray structures, absorption, fluorescence, phosphorescence, and CD spectra of these first generation heli‐acenes are compared to the structure and photophysical properties of pentacene and [7]helicene. A high barrier for the enantio‐enriched M enantiomer of 19,24‐dicyano[7]heli‐D‐anthracene verified its configurational stability at room temperature.