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; Osamu Sato

doi:10.1038/ncomms9810

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, Osamu Sato

Department of Fundamental Organic Chemistry

Research output: Contribution to journal › Article › peer-review

59 Citations (Scopus)

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.

Original language	English
Article number	8810
Journal	Nature communications
Volume	6
DOIs	https://doi.org/10.1038/ncomms9810
Publication status	Published - Nov 4 2015

All Science Journal Classification (ASJC) codes

Chemistry(all)
Biochemistry, Genetics and Molecular Biology(all)
Physics and Astronomy(all)

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

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.",

author = "Su, {Sheng Qun} and Takashi Kamachi and Yao, {Zi Shuo} and Huang, {You Gui} and Yoshihito Shiota and Kazunari Yoshizawa and Nobuaki Azuma and Yuji Miyazaki and Motohiro Nakano and Goro Maruta and Sadamu Takeda and Soonchul Kang and Shinji Kanegawa and Osamu Sato",

note = "Funding Information: This work was partly supported by JSPS KAKENHI Grant Numbers 26104528, 15H01018, 25410071, 24109014 and 15K13710; by Network Joint Research Center for Materials and Devices; and by Nanotechnology Platform Program (Molecule and Material Synthesis) of the Ministry of Education, Culture, Sports, Science and Technology (MEXT). Publisher Copyright: {\textcopyright} 2015 Macmillan Publishers Limited. All rights reserved.",

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doi = "10.1038/ncomms9810",

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T1 - Assembling an alkyl rotor to access abrupt and reversible crystalline deformation of a cobalt(II) complex

AU - Su, Sheng Qun

AU - Kamachi, Takashi

AU - Yao, Zi Shuo

AU - Huang, You Gui

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Azuma, Nobuaki

AU - Miyazaki, Yuji

AU - Nakano, Motohiro

AU - Maruta, Goro

AU - Takeda, Sadamu

AU - Kang, Soonchul

AU - Kanegawa, Shinji

AU - Sato, Osamu

N1 - Funding Information: This work was partly supported by JSPS KAKENHI Grant Numbers 26104528, 15H01018, 25410071, 24109014 and 15K13710; by Network Joint Research Center for Materials and Devices; and by Nanotechnology Platform Program (Molecule and Material Synthesis) of the Ministry of Education, Culture, Sports, Science and Technology (MEXT). Publisher Copyright: © 2015 Macmillan Publishers Limited. All rights reserved.

PY - 2015/11/4

Y1 - 2015/11/4

N2 - 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.

AB - 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.

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

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