Browse by author
Lookup NU author(s): Dr Julien EngORCiD, Dr Thomas PopeORCiD, Professor Thomas PenfoldORCiD
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
External control on chemical reactivity requires understanding the fundamental forces governing reactions at molecular length scales, where interactions with the environment can affect reaction outcomes. In single crystals, reactivity is governed by lattice-constrained molecular packing and unique electrostatic potentials leveraged by specific system-bath interactions that are absent in the solution phase. However, sample depletion and product accumulation have made studies of ultrafast photochemical reactions in crystals challenging. Here, we present the first report of ultrafast spin-vibronic-mediated intersystem crossing (ISC) leading to intramolecular charge transfer in single crystals of binuclear platinum complexes. Ultrafast spectroscopic measurements with advanced time-frequency analysis reveal a 10-fold increase in ISC rate compared to solution phase, arising from lattice effects in tuning the energetics for the singlet–triplet manifolds. Additionally, comparative studies of structurally analogous platinum complexes demonstrate the critical role of bath-controlled tuning of an intermediate state in facilitating efficient ISC. These observations are further supported by quantum-dynamical calculations that predict a systematic variation of ISC rates with the singlet–triplet energy gap, elucidating a general framework for structure-guided control of ISC dynamics through system-bath interactions.
Author(s): Ghosh N, Eng J, Kromer S, Pope TJ, da Silva-Neto ML, Roy S, Pulleri-Vadhyar S, Penfold TJ, Castellano FN, Miller RJD
Publication type: Article
Publication status: Published
Journal: Journal of the American Chemical Society
Year: 2026
Pages: epub ahead of print
Online publication date: 17/06/2026
Acceptance date: 05/06/2026
Date deposited: 24/06/2026
ISSN (print): 0002-7863
ISSN (electronic): 1520-5126
Publisher: American Chemical Society
URL: https://doi.org/10.1021/jacs.6c04591
DOI: 10.1021/jacs.6c04591
ePrints DOI: 10.57711/y7wr-5v28
Data Access Statement: The data supporting the findings of this study are available in the article or Supplementary Information. Additional raw data are available from the corresponding author upon request.
Altmetrics provided by Altmetric
