Thanks to major advances in laser technologies, recent investigations of the ultrafast coupling of nuclear and electronic degrees of freedom (vibronic coupling) have revealed that such coupling plays a crucial role in a wide range of photoinduced reactions in condensed phase supramolecular systems. This paper investigates several new donor-bridge-acceptor charge-transfer molecular assemblies built on a trans-Pt(ii) acetylide core. We also investigate how targeted vibrational excitation with low-energy IR light post electronic excitation can perturb vibronic coupling and affect the efficiency of electron transfer (ET) in solution phase. We compare and contrast properties of a range of donor-bridge-acceptor Pt(ii) trans-acetylide assemblies, where IR excitation of bridge vibrations during UV-initiated charge separation in some cases alters the yields of light-induced product states. We show that branching to multiple product states from a transition state with appropriate energetics is the most rigid condition for the type of vibronic control we demonstrate in our study.
|Number of pages||18|
|Publication status||Published - 2015|