Photoreaction and Molecular Reorientation in a Nanoscaled Film of Poly(methyl 4-(methacryloyloxy)cinnamate) Studied by Two-Dimensional FTIR and UV Correlation Spectroscopy

Photoreaction and photoinduced molecular reorientations in nanoscaled films of poly(methyl 4-(methacryloyloxy)cinnamate) (PMMCi) were investigated through two-dimensional (2D) correlation analyses of their infrared (IR) and ultraviolet (UV) absorption spectra. In the PMMCi film the presence of three distinct chromophore types was evident: isolated trans-isomeric cinnamoyl moieties and parallel and end-to-end cinnamoyl aggregates. Their photoinduced reorientations take place in the following sequence: isolated trans isomeric chromophores → parallel chromophore aggregates → end-to-end chromophore aggregates. It turns out that they react photochemically at different rates. The PMMCi polymer molecules were found to undergo both photoisomerization and photodimerization upon UV irradiation, with the trans−cis isomerization of the isolated trans isomeric cinnamoyl moieties occurring more rapidly than the photodimerization of the cinnamoyl aggregates. Of the photodimerization processes, the reorientation of the...