Molecular dynamics in azobenzene liquid crystal polymer films measured by time-resolved techniquesElectronic supplementary information (ESI) available: Pictures of the film bending, the DSC scan for the film, the principle of the heterodyne transient grating method, and the alignment of the sample and light polarization. See DOI: 10.1039/c4cp00457d

Photo-induced molecular motion in a liquid crystal polymer film including azobenzene was studied by the heterodyne transient grating method. The film was confined in a liquid crystal cell, where it is a photomobile film under free-standing conditions. By observation of the refractive index change induced by a laser pulse, contraction of the film was observed on the order of several hundreds of nanoseconds, and the subsequent reorientation and molecular rotation dynamics were observed from a few microseconds to a hundred milliseconds. Finally, the cis isomer of azobenzene was thermally returned back to the trans isomer in about ten seconds because the film could not be bent in the liquid crystal cell. Since the contraction, reorientation and molecular rotation took place before the cis to trans back-transformation, these processes correspond to the preliminary molecular motion preceding the macroscopic bending of the film. Molecular motion inside a photomobile liquid crystal polymer was investigated by the heterodyne transient grating technique.