Toroidal Interaction and Propeller Chirality of Hexaarylbenzenes. Dynamic Domino Inversion Revealed by Combined Experimental and Theoretical Circular Dichroism Studies
Toroidal Interaction and Propeller Chirality of Hexaarylbenzenes. Dynamic Domino Inversion Revealed by Combined Experimental and Theoretical Circular Dichroism Studies
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DOI：
10.1021/acs.jpclett.6b00179
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发表时间：
2016-03-03
影响因子：
5.7
通讯作者：
Mori, Tadashi
中科院分区：
文献类型：
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作者：
Kosaka, Tomoyo;Inoue, Yoshihisa;Mori, Tadashi
六芳基苯类化合物（HABs）由于其独特的螺旋桨状结构，在液晶、分子胶囊/转子、氧化还原材料、非线性光学材料以及分子导线等材料科学领域具有潜在的应用前景，引起了人们的广泛关注。然而，很少有人注意到他们的螺旋桨手性。通过在HAB的外围引入小的点手性基团，螺旋桨手性被有效地诱导，在圆二色性（CD）光谱中引起强烈的Cotton效应。温度和溶剂极性操纵螺旋桨在溶液中反转的动力学。因此，在极性溶剂和高温下，呼啸的环形变得更加显著，其中径向芳环（螺旋桨叶片）优选相对于中心苯环（C-6核）正交排列，从而使环形相互作用最大化。
Hexaarylbenzenes (HABs) have greatly attracted much attention due to their unique propeller-shaped structure and potential application in materials science, such as liquid crystals, molecular capsules/rotors, redox materials, nonlinear optical materials, as well as molecular wires. Less attention has however been paid to their propeller chirality. By introducing small point-chiral group(s) at the periphery of HABs, propeller chirality was effectively induced, provoking strong Cotton effects in the circular dichroism (CD) spectrum. Temperature and solvent polarity manipulate the dynamics of propeller inversion in solution. As such, whizzing toroids become more substantial in polar solvents and at an elevated temperature, where radial aromatic rings (propeller blades) prefer orthogonal alignment against the central benzene ring (C-6 core), maximizing toroidal interactions.