Hydrostatic Pressure on Toroidal Interaction and Propeller Chirality of Hexaarylbenzenes: Explicit Solvent Effects on Differential Volumes in Methylcyclohexane and Hexane
Hydrostatic Pressure on Toroidal Interaction and Propeller Chirality of Hexaarylbenzenes: Explicit Solvent Effects on Differential Volumes in Methylcyclohexane and Hexane
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DOI：
10.1002/chem.201804688
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发表时间：
2019-02-06
影响因子：
4.3
通讯作者：
Mori, Tadashi
中科院分区：
文献类型：
--
作者：
Kosaka, Tomoyo;Iwai, Satono;Mori, Tadashi
六芳基苯(HABS)具有独特而有效的相互作用，在基础研究和分子导线、传感器、超分子组装等领域具有广泛的应用前景。由于HABS构象之间的动态构象转变，HABS的手性反应受环境因素如溶剂和温度的影响。在这项研究中，详细研究了螺旋桨手性HABS在两种不同溶剂中的压力依赖性。通过CD谱的定量分析确定了两个不同平衡的有效微分体积，在甲基环己烷中，对于H2和H6，从螺旋桨到环状构象(VT-C)的有效微分体积分别为+43和+42 cm(3)摩尔(-1)。在正己烷中，H6的值进一步增大到+72 cm(3)mol(-1)，这是典型的单分子构象变化的最大值。HABS中螺旋桨的手性响应有利于设计更先进的压敏材料。
A unique and effective interaction between the peripheral aromatic blades makes hexaarylbenzenes (HABs) attractive in fundamental research as well as for various applications such as molecular wires, sensors, and supramolecular assemblies. The chiroptical responses of HABs are susceptible to environmental factors such as solvent and temperature owing to the dynamic conformational transitions between the conformers. In this study, pressure dependence on the propeller chiral HABs in two different solvents was studied in detail. The effective differential volumes for two different equilibria were determined by quantitative analyses of CD spectra, affording very large differential volumes from the propeller to toroidal conformer (VT-C) of +43 and +42cm(3)mol(-1), for H2 and H6, respectively, in methylcyclohexane. The value of H6 was further enhanced to +72cm(3)mol(-1) in hexane, the largest value for the typical unimolecular conformational change. Such a response of propeller chirality in HABs is expedient in designing more advanced piezo-sensitive materials.