Symmetry-based rational design for boosting chiroptical responses
Symmetry-based rational design for boosting chiroptical responses
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DOI：
10.1038/s42004-018-0035-x
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发表时间：
2018-07
影响因子：
5.9
通讯作者：
Hiroki Tanaka;Mina Ikenosako;Yuka Kato;M. Fujiki;Y. Inoue;Tadashi Mori
中科院分区：
文献类型：
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作者：
Hiroki Tanaka;Mina Ikenosako;Yuka Kato;M. Fujiki;Y. Inoue;Tadashi Mori
手性分子在先进材料和技术中发挥着不可缺少的作用。然而，没有传统的，但可靠的逻辑策略可用于设计所需的手性分子的手性性质。本文以六螺旋烯为原型，提出了一种合理排列多个手性单元以提高热响应的通用方案。在这个概念验证研究中，我们将两个六螺旋体排列在不同的方向上，并通过理论计算来预测x形和s形双六螺旋体的最佳热学性能。我们合成并光学解析了这两种双六螺旋烯，并表明它们的圆二色性和圆偏振发光强度增加了两倍以上，实验验证了该方案。从理论上讲，增强的chiropal响应可归因于六螺旋烷的电跃迁偶极矩和磁跃迁偶极矩。进一步讨论了设计先进分子和超分子手性材料的指导原则。
Chiral molecules play indispensable roles in advanced materials and technologies. Nevertheless, no conventional, yet reliable logical strategies are available for designing chiral molecules of desired chiroptical properties. Here, we propose a general protocol for rationally aligning multiple chiral units to boost the chiroptical responses, using hexahelicene as a prototype. In this proof-of-concept study, we align two hexahelicenes in various orientations and examine by theoretical calculations to predict the best chiroptical performance for X-shaped and S-shaped double hexahelicenes. We synthesize and optically resolve both double hexahelicenes and show that they exhibit more than a twofold increase in intensity of circular dichroism and circularly polarized luminescence, experimentally validating the protocol. The enhanced chiroptical responses are theoretically assignable to the electric and magnetic transition dipole moments of component hexahelicenes aligned in the correct symmetry. A guiding principle for designing advanced molecular and supramolecular chiral materials is further discussed.