Assembling an alkyl rotor to access abrupt and reversible crystalline deformation of a cobalt(II) complex

Sheng-Qun Su, Takashi Kamachi, Zi-Shuo Yao, You-Gui Huang, Yoshihito Shiota, Kazunari Yoshizawa, Nobuaki Azuma, Yuji Miyazaki, Motohiro Nakano, Goro Maruta, Sadamu Takeda, Soonchul Kang, Shinji Kanegawa and Osamu Sato ()
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Sheng-Qun Su: Institute for Materials Chemistry and Engineering, Kyushu University
Takashi Kamachi: Institute for Materials Chemistry and Engineering, Kyushu University
Zi-Shuo Yao: Institute for Materials Chemistry and Engineering, Kyushu University
You-Gui Huang: Institute for Materials Chemistry and Engineering, Kyushu University
Yoshihito Shiota: Institute for Materials Chemistry and Engineering, Kyushu University
Kazunari Yoshizawa: Institute for Materials Chemistry and Engineering, Kyushu University
Nobuaki Azuma: Research Center for Structural Thermodynamics, Graduate School of Science, Osaka University
Yuji Miyazaki: Research Center for Structural Thermodynamics, Graduate School of Science, Osaka University
Motohiro Nakano: Research Center for Structural Thermodynamics, Graduate School of Science, Osaka University
Goro Maruta: Faculty of Science, Hokkaido University
Sadamu Takeda: Faculty of Science, Hokkaido University
Soonchul Kang: Institute for Materials Chemistry and Engineering, Kyushu University
Shinji Kanegawa: Institute for Materials Chemistry and Engineering, Kyushu University
Osamu Sato: Institute for Materials Chemistry and Engineering, Kyushu University

Nature Communications, 2015, vol. 6, issue 1, 1-7

Abstract: Abstract Harnessing molecular motion to reversibly control macroscopic properties, such as shape and size, is a fascinating and challenging subject in materials science. Here we design a crystalline cobalt(II) complex with an n-butyl group on its ligands, which exhibits a reversible crystal deformation at a structural phase transition temperature. In the low-temperature phase, the molecular motion of the n-butyl group freezes. On heating, the n-butyl group rotates ca. 100° around the C–C bond resulting in 6–7% expansion of the crystal size along the molecular packing direction. Importantly, crystal deformation is repeatedly observed without breaking the single-crystal state even though the shape change is considerable. Detailed structural analysis allows us to elucidate the underlying mechanism of this deformation. This work may mark a step towards converting the alkyl rotation to the macroscopic deformation in crystalline solids.

Date: 2015
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DOI: 10.1038/ncomms9810

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