Crystalline-State <i>Z,E-</i>Photoisomerization of a Series of (<i>Z</i>,<i>E</i>,<i>Z</i>)-1,6-Diphenylhexa-1,3,5-triene 4,4‘-Dicarboxylic Acid Dialkyl Esters. Chain Length Effects on the Crystal Structure and Photoreactivity^†

Crystalline-state Z,E-photoisomerization of a series of (Z,E,Z)-1,6-diphenylhexa-1,3,5-triene 4,4‘-dicarboxylic acid dialkyl (R) esters [(Z,E,Z)-1a, R = Me; (Z,E,Z)-1b, R = Et; (Z,E,Z)-1c, R = n-Pr; (Z,E,Z)-1d, R = n-Bu] was investigated. All Z,E,Z isomers underwent one-way isomerization to the corresponding E,E,E isomers. The reaction efficiency was strongly enhanced as the length of the alkyl chain increased. Single-crystal X-ray analyses of (Z,E,Z)-1a−d showed that the alkyl chain part of the crystals became larger as the chain length increased. The conformational flexibility of the alkyl chains made the large change in the triene geometry in the lattice possible, leading to the enhancement of the photoreactivity in the crystalline state.