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首页> 外文期刊>RSC Advances >A crystalline molecular gyrotop with germanium junctions between a phenylene rotor and alkyl spokes
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A crystalline molecular gyrotop with germanium junctions between a phenylene rotor and alkyl spokes

机译：在亚苯基转子和烷基辐条之间具有锗结的结晶分子陀螺仪

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摘要

Macrocage molecules with a bridged phenylene have been reported as molecular gyrotops, in which the phenylene moiety can rotate even in the crystalline state. The roles of the atoms in the junctions between the rotor and spokes in molecular gyrotops have not been clarified well. In this study, a molecular gyrotop with germanium junctions was designed and synthesized, and the differences between the properties of the germanium and silicon derivatives were discussed. Notably, a structural isomer of the cage, which is not formed in the synthesis of the silicon derivative, was formed during the synthesis of the germanium derivative. Because the long Ge-C(Ph) bond length (1.958(4) angstrom) was observed in the crystal structure of the germanium derivative as compared to the Si-C(Ph) bond length (1.885(2) angstrom) of the silicon derivative, the activation energy for the rotation of the phenylene moiety inside the crystalline state of the germanium derivative (8.0 kcal mol(-1)) was lower than that of the silicon derivative (9.0 kcal mol(-1)). Similar tendencies of temperature-dependent optical properties of the single crystal, i.e., birefringence (Delta n), were observed between the germanium and the silicon derivatives, but the temperatures and magnitudes of the discontinuous change in the birefringence were different.
机译：据报道具有桥联亚苯基的巨笼分子是分子陀螺仪，其中亚苯基部分即使在结晶状态下也可以旋转。分子陀螺仪中转子和轮辐之间的连接处原子的作用尚不清楚。在这项研究中，设计并合成了具有锗结的分子陀螺仪，并讨论了锗和硅衍生物的性能差异。值得注意的是，在锗衍生物的合成过程中形成了在硅衍生物的合成中未形成的笼的结构异构体。因为与硅的Si-C（Ph）键长（1.885（2）埃）相比，锗衍生物的晶体结构中观察到长的Ge-C（Ph）键长（1.958（4）埃）衍生物，锗衍生物（8.0 kcal mol（-1））的结晶状态内亚苯基部分旋转的活化能低于硅衍生物（9.0 kcal mol（-1））。在锗和硅衍生物之间观察到单晶的随温度变化的光学特性的相似趋势，即双折射（Δn），但是双折射的不连续变化的温度和大小不同。

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