Anisotropic Thermal Expansion as the Source of Macroscopic and Molecular Scale Motion in Phosphorescent Amphidynamic Crystals
Anisotropic Thermal Expansion as the Source of Macroscopic and Molecular Scale Motion in Phosphorescent Amphidynamic Crystals
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DOI：
10.1002/anie.201909048
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发表时间：
2019-10-24
影响因子：
16.6
通讯作者：
Garcia-Garibay, Miguel A.
中科院分区：
文献类型：
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作者：
Jin, Mingoo;Yamamoto, Sho;Garcia-Garibay, Miguel A.
在这里，我们报告了一个晶体分子转子与旋转调制的三重态发射，显示宏观动力学的晶体移动和/或跳跃的形式，也被称为显着的效果。分子转子2的中心1，4-二乙炔基-2，3-二氟亚苯基旋转体连接到两个金（I）节点，通过分子间金（I）-金（I）相互作用结晶为无限一维链。旋转运动改变了中心亚苯基的取向，改变了相邻发色团之间的电子通信，从而改变了发射强度。2的晶体显示出大的和可逆的热膨胀/压缩各向异性，这解释了1）分子水平旋转动力学中的非线性Arrhenius行为，其与2）发射的变化相关，并决定3）宏观晶体运动。分子转子类似物3具有与2相似的性质，这表明了在分子和宏观尺度上控制机械性质的一般化方法。
Herein we report a crystalline molecular rotor with rotationally modulated triplet emission that displays macroscopic dynamics in the form of crystal moving and/or jumping, also known as salient effects. Molecular rotor 2 with a central 1,4-diethynyl-2,3-difluorophenylene rotator linked to two gold(I) nodes, crystalizes as infinite 1D chains through intermolecular gold(I)-gold(I) interactions. The rotational motion changes the orientation of the central phenylene, changing the electronic communication between adjacent chromophores, and thus the emission intensities. Crystals of 2 showed the large and reversible thermal expansion/compression anisotropy, which accounts for 1) a nonlinear Arrhenius behavior in molecular-level rotational dynamics, which correlates with 2) changes in emission, and determines 3) the macroscopic crystal motion. A molecular rotor analogue 3 has properties similar to those of 2, suggesting a generalized way to control mechanical properties at molecular and macroscopic scales.