Rapid and reversible shape changes of molecular crystals on photoirradiation : Abstract : Nature

Nature 446, 778-781 (12 April 2007) | doi:10.1038/nature05669; Received 4 October 2006; Accepted 10 February 2007

Rapid and reversible shape changes of molecular crystals on photoirradiation

Seiya Kobatake¹, Shizuka Takami², Hiroaki Muto², Tomoyuki Ishikawa¹ & Masahiro Irie²

Department of Applied Chemistry, Graduate School of Engineering, Osaka City University, Sugimoto 3-3-138, Sumiyoshi-ku, Osaka 558-8585, Japan
Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, Hakozaki 6-10-1, Fukuoka 812-8581, Japan

Correspondence to: Masahiro Irie² Correspondence and requests for materials should be addressed to M.I. (Email: irie@cstf.kyushu-u.ac.jp).

The development of actuators based on materials that reversibly change shape and/or size in response to external stimuli has attracted interest for some time¹. A particularly intriguing possibility is offered by light-responsive materials, which allow remote operation without the need for direct contact to the actuator. The photo-response of these materials is based on the photoisomerization of constituent molecules (typically trans–cis isomerization of azobenzene chromophores), which gives rise to molecular motions and thereby deforms the bulk material. This effect has been used to create light-deformable polymer films and gels^2,^3,^4,^5,^6,^7,^8,^9,¹⁰, but the response of these systems is relatively slow. Here we report that molecular crystals based on diarylethene chromophores and with sizes ranging from 10 to 100 micrometres exhibit rapid and reversible macroscopic changes in shape and size induced by ultraviolet and visible light. We find that on exposure to ultraviolet light, a single crystal of 1,2-bis(2-ethyl-5-phenyl-3-thienyl)perfluorocyclopentene changes from a square shape to a lozenge shape, whereas a rectangular single crystal of 1,2-bis(5-methyl-2-phenyl-4-thiazolyl)perfluorocyclopentene contracts by about 5–7 per cent. The deformed crystals are thermally stable, and switch back to their original state on irradiation with visible light. We find that our crystals respond in about 25 microseconds (that is, about five orders of magnitude faster than the response time of the azobenzene-based polymer systems^7,^8,^9,¹⁰) and that they can move microscopic objects, making them promising materials for possible light-driven actuator applications.

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