Tripmultiplet-state dynamics of manganese(III) porphyrin fabricated into PVC film

Luminescence lifetimes of anion complexes of manganese(III) porphyrins incorporated in the PVC polymer film were investigated by the time-correlated single photon counting (TCSPC) method. The tripquintet state lifetimes (tens of picoseconds) which had been measured in the solution phase were reduced to the hundreds of picoseconds regime in the polymer solid phase when the internal motions of porphyrin moieties are restricted by the PVC polymer matrix. The main effects of bulkier anion ligation on photophysical properties were the increment of effective void volume. The increase of lifetime constants in the stiff polymer matrix was largest in case of the smallest anion ligation due to the restriction of internal motion induced by local polymer structure having the smaller void volume.