Crystal engineering of photochromic diarylethene single crystals.
Photochromic performance of diarylethene single crystals was controlled by crystal engineering using non-covalent aromatic-aromatic interactions as the directional intermolecular force. A diarylethene derivative with two pentafluorophenyl groups, 1,2-bis(2-methyl-5-pentafluorophenyl-3-thienyl)perfluorocyclopentene (1a), formed stoichiometric co-crystals with benzene (Bz) and naphthalene (Np) by aryl-perfluoroaryl interactions. Face-to-face pi-stacking interactions between the pentafluorophenyl groups of 1a and the aromatic molecules are responsible for 2:1 and 1:1 stoichiometric compositions in 1a/Bz and 1a/Np co-crystals, respectively. The diarylethene underwent thermally stable and photoreversible photochromic reactions in a homo-crystal of 1a and co-crystals 1a/Bz and 1a/Np. The absorption spectra of the photogenerated closed-ring isomers varied depending on the conformation of the diarylethene molecules packed in the crystals. The diarylethene 1a also formed 1:1 stoichiometric co-crystals with different kinds of diarylethenes, 1,2-bis(2-ethyl-5-phenyl-3-thienyl)perfluorocyclopentene (2a) and 1,2-bis[2-methyl-5-(1-naphthyl)-3-thienyl]perfluorocyclopentene (3a). Both co-crystals 1a/2a and 1a/3a showed photochromism. Although 1a, 2a, and 3a underwent efficient photocyclization reactions in their homo-crystals, highly selective photocyclization reactions of 2a or 3a were observed in the co-crystals. The selective reactions were confirmed by HPLC and X-ray crystallography. Excited energy transfers from 1a to 2a and from 1a to 3a are considered to occur and cause the selective reactions.
Morimoto
Masakazu
M
Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, Hakozaki 6-10-1, Higashi-ku, Fukuoka 812-8581, Japan.
Kobatake
Seiya
S
Irie
Masahiro
M
D003460:Crystallization; D018360:Crystallography, X-Ray; D005030:Ethylenes / Q000138:chemical synthesis / Q000737:chemistry*; D006841:Hydrocarbons, Aromatic / Q000138:chemical synthesis / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D010777:Photochemistry; D013237:Stereoisomerism
D005030:Ethylenes; D006841:Hydrocarbons, Aromatic