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

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...

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Bibliographic Details
Published in:The journal of physical chemistry letters 2021-07, Vol.12 (29)
Main Authors: Kim, Pyosang, Valentine, Andrew J. S., Roy, Subhangi, Mills, Alexis W., Chakraborty, Arnab, Castellano, Felix N., Li, Xiaosong, Chen, Lin X.
Format: Article
Language:English
Subjects:
computational chemistry
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ligands
oligomers
oscillation
probes
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Summary: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.
ISSN:1948-7185
1948-7185