Thermochromism in an organic crystal based on the coexistence of sigma- and pi-dimers.

Thermochromism in an organic crystal based on the coexistence of sigma- and pi-dimers. Research Abstract Details 

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Thermochromism in an organic crystal based on the coexistence of sigma- and pi-dimers. Abstract Text:

Yasushi Morita,Shuichi Suzuki,Kozo Fukui,Shigeaki Nakazawa,Hiroshi Kitagawa,Hideo Kishida,Hiroshi Okamoto,Akira Naito,Akiko Sekine,Yuji Ohashi,Motoo Shiro,Katsunari Sasaki,Daisuke Shiomi,Kazunobu Sato,Takeji Takui,Kazuhiro Nakasuji,Yasushi Morita,Shuichi Suzuki,Kozo Fukui,Shigeaki Nakazawa,Hiroshi Kitagawa,Hideo Kishida,Hiroshi Okamoto,Akira Naito,Akiko Sekine,Yuji Ohashi,Motoo Shiro,Katsunari Sasaki,Daisuke Shiomi,Kazunobu Sato,Takeji Takui,Kazuhiro Nakasuji,Yasushi Morita,Shuichi Suzuki,Kozo Fukui,Shigeaki Nakazawa,Hiroshi Kitagawa,Hideo Kishida,Hiroshi Okamoto,Akira Naito,Akiko Sekine,Yuji Ohashi,Motoo Shiro,Katsunari Sasaki,Daisuke Shiomi,Kazunobu Sato,Takeji Takui,Kazuhiro Nakasuji,

Transition-metal complexes and organic radical molecules can be used to make electric conductors and ferromagnets, the optical properties of which can be controlled by changing temperature and are used as molecular switches and sensors. Whereas a number of organic radicals in solution show temperature-dependent optical properties, such behaviour in crystalline forms is more rare. Here, we show a fully reversible continuous thermochromism with a unique mechanism in purely organic crystals of diazaphenalenyl radical. This behaviour is based on changes in the diazaphenalenyl dimers coexisting in the crystal. From the X-ray crystal structure analyses and temperature-dependent visible spectra, we conclude the presence of a thermal equilibrium between sigma-bonded and pi-bonded dimers, which are separated by 2.62(6) kcal mol(-1). This conclusion is supported by room-temperature electron spin resonance spectra of the solid, which showed signals that are attributable to a thermally accessible triplet state of the pi-dimer structure. This proves the coexistence of two dimers of different bonding natures in the crystal, causing it to demonstrate thermometer-like behaviour.

Thermochromism in an organic crystal based on the coexistence of sigma- and pi-dimers. Publishing Authors By Initials

Y Morita,S Suzuki,K Fukui,S Nakazawa,H Kitagawa,H Kishida,H Okamoto,A Naito,A Sekine,Y Ohashi,M Shiro,K Sasaki,D Shiomi,K Sato,T Takui,K Nakasuji,Y Morita,S Suzuki,K Fukui,S Nakazawa,H Kitagawa,H Kishida,H Okamoto,A Naito,A Sekine,Y Ohashi,M Shiro,K Sasaki,D Shiomi,K Sato,T Takui,K Nakasuji,Y Morita,S Suzuki,K Fukui,S Nakazawa,H Kitagawa,H Kishida,H Okamoto,A Naito,A Sekine,Y Ohashi,M Shiro,K Sasaki,D Shiomi,K Sato,T Takui,K Nakasuji,

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Thermochromism in an organic crystal based on the coexistence of sigma- and pi-dimers. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Nature materials

VOLUME: 7

Page Numbers: 48-51

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ISSN: 1476-1122

DAY: 2

MONTH: 12

YEAR: 2007

Thermochromism in an organic crystal based on the coexistence of sigma- and pi-dimers. Information

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LANGUAGE: eng

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Grant and Affiliation Information for Thermochromism in an organic crystal based on the coexistence of sigma- and pi-dimers.

AFFILIATION: [1] Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan [2] PRESTO, Japan Science and Technology Agency, Kawaguchi, Saitama 332-0012, Japan.

Country: England

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MEDLINETA: Nat Mater

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