TY - JOUR
T1 - Ultrafast Excited-State Dynamics of Photoluminescent Pt(II) Dimers Probed by a Coherent Vibrational Wavepacket
AU - Kim, Pyosang
AU - Valentine, Andrew J.S.
AU - Roy, Subhangi
AU - Mills, Alexis W.
AU - Chakraborty, Arnab
AU - Castellano, Felix N.
AU - Li, Xiaosong
AU - Chen, Lin X.
N1 - Funding Information:
This work has been supported by the National Science Foundation (Grant CHE-1955806 to L.X.C. and Grant CHE-1955795 to F.N.C.). The computational work and P.K. and L.X.C. is supported in part by the Ultrafast Initiative of the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, through Argonne National Laboratory under Contract DE-AC02-06CH11357. The development of the computational method for simulating excited-state dynamics is supported by the National Science Foundation (Grant CHE-1856210 to X.L.).
Publisher Copyright:
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PY - 2021/7/29
Y1 - 2021/7/29
N2 - 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.
AB - 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.
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U2 - 10.1021/acs.jpclett.1c01289
DO - 10.1021/acs.jpclett.1c01289
M3 - Article
C2 - 34270259
AN - SCOPUS:85111545690
SN - 1948-7185
VL - 12
SP - 6794
EP - 6803
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 29
ER -