Ultrafast Excited-State Dynamics of Photoluminescent Pt(II) Dimers Probed by a Coherent Vibrational Wavepacket

Pyosang Kim, Andrew J.S. Valentine, Subhangi Roy, Alexis W. Mills, Arnab Chakraborty, Felix N. Castellano, Xiaosong Li, Lin X. Chen*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

21 Scopus citations


Intricate potential energy surfaces (PESs) of some transition metal complexes (TMCs) pose challenges in mapping out initial excited-state pathways that could influence photochemical outcomes. Ultrafast intersystem crossing (ISC) dynamics of four structurally related platinum(II) dimer complexes were examined by detecting their coherent vibrational wavepacket (CVWP) motions of Pt-Pt stretching mode in the metal-metal-to-ligand-charge-transfer excited states. Structurally dependent CVWP behaviors (frequency, dephasing time, and oscillation amplitudes) were captured by femtosecond transient absorption spectroscopy, analyzed by short-time Fourier transformation, and rationalized by quantum mechanical calculations, revealing dual ISC pathways. The results suggest that the ligands could fine-tune the PESs to influence the proximity of the conical intersections of the excited states with the Franck-Condon state and thus to control the branching ratio of the dual ISC pathways. This comparative study presents future opportunities in control excited-state trajectories of TMCs via ligand structures.

Original languageEnglish (US)
Pages (from-to)6794-6803
Number of pages10
JournalJournal of Physical Chemistry Letters
Issue number29
StatePublished - Jul 29 2021

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry


Dive into the research topics of 'Ultrafast Excited-State Dynamics of Photoluminescent Pt(II) Dimers Probed by a Coherent Vibrational Wavepacket'. Together they form a unique fingerprint.

Cite this