Unraveling Molecular Design Principle of Ferroelasticity in Organic Semiconductor Crystals with Two-Dimensional Brickwork Packing
Unraveling Molecular Design Principle of Ferroelasticity in Organic Semiconductor Crystals with Two-Dimensional Brickwork Packing
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DOI：
10.1021/acs.chemmater.2c02534
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发表时间：
2022-12
影响因子：
8.6
通讯作者：
Sang Kyu Park;Hongtao Sun;M. Bernhardt;Kyoungtae Hwang;J. Anthony;K. Zhao;Ying Diao
中科院分区：
文献类型：
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作者：
Sang Kyu Park;Hongtao Sun;M. Bernhardt;Kyoungtae Hwang;J. Anthony;K. Zhao;Ying Diao
有机单晶的铁弹性最近引起了人们极大的研究兴趣。它是响应机械应力的可逆孪晶转变，赋予晶体材料显着的变形能力，同时允许材料保留其固有的功能特性。铁弹性的这些吸引人的属性有望实现高性能、超柔性、可拉伸的单晶（光电）电子产品。在这项工作中，我们揭示了三烷基甲硅烷基并苯（TAS-并苯）晶体的铁弹性转变的结构标准，该晶体由于二维电子耦合而被称为高性能有机半导体材料。这项研究表明，只有相邻芳香核和 TAS 侧链互锁均不存在二维砖砌堆积时，才能实现铁弹性转变。这是因为芳香核联锁阻止了结构转变过程中的协同分子滑动和旋转，而侧链联锁阻止了 TAS 侧链重新配置，而TAS侧链重构是缓解协同分子运动时发生的空间应变所必需的。本文揭示的分子排列和铁弹性转变能力的相关性将有助于深入了解固有柔性有机半导体晶体的材料设计原理。
Ferroelasticity of organic single crystals has recently attracted great research interest. It is a reversible twinning transition in response to mechanical stress that imparts remarkable deformability to crystalline materials while allowing materials to retain their inherent functional properties. These appealing attributes of ferroelasticity promise high-performance ultraflexible, stretchable single-crystalline (opto-) electronics. In this work, we unravel structural criteria for ferroelastic transition of trialkylsilyl-acene (TAS-acene) crystals, which are known as high-performance organic semiconductor materials owing to two-dimensional electronic coupling. This study unveils that ferroelastic transitions are achievable only if two-dimensional brickwork packing is absent from both neighboring aromatic core and TAS side-chain interlocking. This is because aromatic core interlocking prevents cooperative molecular gliding and rotation during structural transition, while side-chain interlocking prevents TAS side-chain reconfiguration necessary for relieving steric strain occurring upon the cooperative molecular motions. The correlation of molecular arrangement and ferroelastic transition capability revealed herein will provide insight into the material design principle of inherently flexible organic semiconductor crystals.