Photophysics of Monodisperse Platinum-Acetylide Oligomers: Delocalization in the Singlet and Triplet Excited States

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Abstract
A series of monodisperse Pt-acetylide polymers that contain the [−C⋮C−(p-C6H4)−C⋮C−(t-Pt(PBu3)2)−]n repeat unit has been prepared for n = 1, 2, 3, 4, 5, and 7. The photophysical properties of the series provide information concerning the relationship between the oligomer length and delocalization in the singlet and triplet excited states of the π-conjugated electron system. The results imply that the singlet excited state is delocalized over approximately 6 repeat units; however, the triplet state is considerably more localized. The triplet energy is almost invariant with oligomer length, but the phosphorescence spectra and triplet nonradiative decay rates indicate that the electron-vibrational coupling in the triplet state decreases with increasing oligomer length.