title: Ultrafast charge transfer dynamics in supramolecular Pt(II) donor-bridge-acceptor assemblies: the effect of vibronic coupling.
abstract: 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.
authors.affiliation: Department of Chemistry, University of Sheffield, Brook Hill, Sheffield, S3 7HF, UK. Julia.Weinstein@sheffield.ac.uk.
authors.forename: Paul A
authors.initials: PA
authors.lastname: Scattergood
authors.affiliation: Department of Chemistry, University of Sheffield, Brook Hill, Sheffield, S3 7HF, UK. Julia.Weinstein@sheffield.ac.uk.
authors.forename: Milan
authors.initials: M
authors.lastname: Delor
authors.affiliation: Department of Chemistry, University of Sheffield, Brook Hill, Sheffield, S3 7HF, UK. Julia.Weinstein@sheffield.ac.uk and Central Laser Facility, Science and Technology Facilities Council, Harwell Science and Innovation Campus, Rutherford Appleton Laboratory, Oxfordshire OX11 0QX, UK.
authors.forename: Igor V
authors.initials: IV
authors.lastname: Sazanovich
authors.affiliation: Central Laser Facility, Science and Technology Facilities Council, Harwell Science and Innovation Campus, Rutherford Appleton Laboratory, Oxfordshire OX11 0QX, UK.
authors.forename: Michael
authors.initials: M
authors.lastname: Towrie
authors.affiliation: Department of Chemistry, University of Sheffield, Brook Hill, Sheffield, S3 7HF, UK. Julia.Weinstein@sheffield.ac.uk.
authors.forename: Julia A
authors.initials: JA
authors.lastname: Weinstein