Molecular Gyrotops with a Five-Membered Heteroaromatic Ring: Synthesis, Temperature-Dependent Orientation of Dipolar Rotors inside the Crystal, and its Birefringence Change

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• 作者：Toshiyuki Masuda ; Junko Arase ; Yusuke Inagaki ; Masatoshi Kawahata ; Kentaro Yamaguchi ; Takashi Ohhara ; Akiko Nakao ; Hiroyuki Momma ; Eunsang Kwon ; Wataru Setaka
• 刊名：Crystal Growth & Design
• 出版年：2016
• 出版时间：August 3, 2016
• 年：2016
• 卷：16
• 期：8
• 页码：4392-4401
• 全文大小：638K
• 年卷期：0
• ISSN：1528-7505

文摘

Three-dimensional arrays of dipolar rotors were constructed as single crystals of molecular gyrotops, which are macrocage molecules with a bridged dipolar rotor. In this study, we synthesized novel molecular gyrotops with a five-membered heteroring, i.e., furan-diyl (1), thiophene-diyl (2), and selenophene-diyl (3), and investigated the temperature-dependent orientation and rotation of the dipolar rotors inside the crystal. Unfortunately, furan derivative 1 did not crystallize; however, crystal structures of the other molecular gyrotops, i.e., 2 and 3, showed three-dimensional arrays of dipolar rotors. Thermal order–disorder transitions of the dipolar rotor orientation inside the crystal were observed in 2 and 3 with the transition temperature in selenophene derivative 3 being lower than that of thiophene derivative 2. This may be ascribed to subtle differences in the molecular structure, e.g., the intersection angle between two Si–C(aryl) bonds corresponding to the rotation axis. In accordance with the thermal change of the crystal structure, temperature-dependent optical properties of a single crystal were observed by analysis of birefringence of the crystal.