Switches, and Actuators Masahiro Irie,*,† Tuyoshi Fukaminato,‡ Kenji Matsuda, and Seiya Kobatake †Research Center for Smart Molecules, Rikkyo University, Nishi-Ikebukuro 3-34-1, Toshima-ku, Tokyo 171-8501, Japan ‡Research Institute for Electronic Science, Hokkaido University, N20, W10, Kita-ku, Sapporo 001-0020, Japan Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan Department of Applied Chemistry, Graduate School of Engineering, Osaka City University, Sugimoto 3-3-138, Sumiyoshi-ku, Osaka 558-8585, Japan

Photochromism of Diarylethene Molecules and Crystals: Memories, Switches, and Actuators

The surface morphology of a diarylethene single crystal [1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)perfluorocyclopentene] determined by atomic force microscopy changed reversibly upon photoirradiation. The crystal underwent a thermally irreversible but photochemically reversible color change (colorless to blue) upon alternate irradiation with ultraviolet (wavelength λ = 366 nm) and visible (λ > 500 nm) light that drove reversible photocyclization reactions. Upon irradiation with 366-nm light, new steps appeared on the (100) single-crystalline surface that disappeared upon irradiation with visible light (λ > 500 nm). The step height, about 1 nm, corresponds to one molecular layer. Irradiation with 366-nm light formed valleys on the (010) surface that also disappeared by bleaching upon irradiation with visible light (λ > 500 nm). The surface morphological changes can be explained by the molecular structural changes of diarylethenes regularly packed in the single crystal. These crystals could potentially be used as photodriven nanometer-scale actuators.

https://science.sciencemag.org/content/sci/291/5509/1769.full.pdf

Reversible Surface Morphology Changes of a Photochromic Diarylethene Single Crystal by Photoirradiation

Photochromic reactions of diarylethene derivatives were detected at a single-molecule level by using a fluorescence technique. Fluorescent photoswitching molecules in which photochromic diarylethene and fluorescent bis(phenylethynyl)anthracene units are linked through an adamantyl spacer were synthesized, and switching of fluorescence upon irradiation with UV and visible light was followed in solution as well as on polymer films at the single-molecule level. Although in solution the fluorescence intensity gradually changed upon irradiation with UV and visible light, digital on/off switching between two discrete states was observed at the single-molecule level. The “on”- and “off”-times were dependent on the power of UV and visible light. When the power of UV and visible light was increased, the average on- and off-times became short in proportion to the reciprocal power of the light. The response-times were found to show distribution. The distribution of the on- and off-times is considered to reflect the ...

Digital photoswitching of fluorescence based on the photochromism of diarylethene derivatives at a single-molecule level.

The photomechancial effect of a rectangular plate two-component cocrystal composed of a photochromic diarylethene derivative, 1,2-bis(2-methyl-5-(1-naphthyl)-3-thienyl)perfluorocyclopentene (1o), and perfluoronaphthalene (FN) has been examined. The crystal of 1o·FN with the size of 1-5 mm in length exhibits reversible bending motion upon alternate irradiation with ultraviolet (UV) and visible light. The reversible bending could be repeated over 250 times. In situ X-ray crystallographic analysis revealed that the deformation of the crystal is due to the elongation of the b-axis of the unit cell, which corresponds to the long axis of the plate crystal, induced by the shape change of component diarylethene molecules upon photocyclization. The bending motion was observed even at 4.7 K, and dynamic measurement of the bending proved that the anisotropic expansion of the crystal takes place in the microsecond time scale at the low temperature. Molecular crystal cantilevers made of 1o·FN can lift metal balls, the weight of which is 200-600 times heavier than the weight of the crystal, upon UV irradiation. The maximum stress generated by UV irradiation was estimated to be 44 MPa, which is 100 times larger than that of muscles (∼0.3 MPa) and comparable to that of piezoelectric crystals, such as lead zirconate titanate (PZT) (∼50 MPa).

A Diarylethene Cocrystal that Converts Light into Mechanical Work

Single-crystalline photochromism of diarylethenes: reactivity–structure relationship

1,2-Bis(2-methyl-5-phenyl-3-thienyl)perfluorocyclopentene (1a) and their derivatives, 1,2-bis(2-methyl-5-p-tolyl-3-thienyl)perfluorocyclopentene (2a) and 1,2-bis(2-methyl-5-p-tert-butylphenyl-3-thienyl)perfluorocyclopentene (3a), were found to undergo reversible photochromic reactions in the single-crystalline phase. Upon irradiation with 366 nm light the single crystals turned blue. The blue colored crystals returned to colorless by irradiation with visible light (λ > 480 nm). The substituents at para positions of the phenyl groups did not affect the rates of photocyclization reactions both in the single-crystalline phase and in hexane. Activation energies of the photocyclization reactions were almost zero. On the other hand, activation energies as much as 5−10 kJ mol-1 were observed in the photocycloreversion reactions in the single-crystalline phase. These values were smaller than those observed in solution, ca. 16 kJ mol-1. Slow thermal cycloreversion reaction of the closed-ring isomer (1b) was observ...

Photochromism of 1,2-Bis(2-methyl-5-phenyl-3-thienyl)perfluorocyclopentene in a Single-Crystalline Phase

A diarylethene derivative with two pentafluorophenyl groups, 1,2-bis(2-methyl-5-pentafluorophenyl-3-thienyl)perfluorocyclopentene (1a), was synthesized in an attempt to prepare photochromic single crystals with well-controlled photochromic properties by utilizing intermolecular noncovalent aryl−perfluoroaryl interactions. Compound 1a formed stoichiometric cocrystals with aromatic hydrocarbons, benzene (Bz) and naphthalene (Np), based on aryl−perfluoroaryl interactions. In crystal 1a/Bz (1a:Bz = 2:1), a linear chain structure was constructed, in which each benzene molecule is sandwiched between pentafluorophenyl rings of two 1a molecules. In crystal 1a/Np (1a:Np = 1:1), a discrete sandwiched structure was formed, in which two 1a molecules sandwich two naphthalene molecules between its pentafluorophenyl groups. In the 1a, 1a/Bz, and 1a/Np crystals, the diarylethene molecules underwent photochromic reactions. Absorption properties of the photogenerated closed-ring isomers were different from each other depen...

and Seiya Kobatake

Papers

Photochromism of 1,2-Bis(2-methyl-5-phenyl-3-thienyl)perfluorocyclopentene in a Single-Crystalline Phase

Aryl-perfluoroaryl interaction in photochromic diarylethene crystals