Deciphering Charge Transfer Processes in Transition Metal Complexes from the Perspective of Ultrafast Electronic and Nuclear Motions

Mara, Michael W.; Weingartz, Nicholas P.; Leshchev, Denis; Hsu, Darren; Valentine, Andrew; Mills, Alexis; Roy, Subhangi; Chakraborty, Arnab; Kim, Pyosang; Biasin, Elisa; Haldrup, Kristoffer; Kirschner, Matthew S.; Rimmerman, Dolev; Chollet, Matthieu; Glownia, James M.; van Driel, Timothy B.; Castellano, Felix N.; Li, Xiaosong; Chen, Lin X.

doi:10.1021/acs.jpclett.4c00735

Title: Deciphering Charge Transfer Processes in Transition Metal Complexes from the Perspective of Ultrafast Electronic and Nuclear Motions

Journal Article · 08 May 2024 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.4c00735 · OSTI ID:2505042

^[1]; Weingartz, Nicholas P. ^[2];

^[2];

^[2]; Valentine, Andrew ^[3]; Mills, Alexis ^[3]; Roy, Subhangi ^[4]; Chakraborty, Arnab ^[4]; Kim, Pyosang ^[1]; Biasin, Elisa ^[5]; Haldrup, Kristoffer ^[6];

^[2];

^[5]; Glownia, James M. ^[5];

^[5];

^[4];

^[3];

^[7]

Argonne National Laboratory (ANL), Argonne, IL (United States)
Northwestern Univ., Evanston, IL (United States)
Univ. of Washington, Seattle, WA (United States)
North Carolina State University, Raleigh, NC (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Physics Department, Technical Institute of Denmark, 2800 Kongens Lyngby, Denmark
Argonne National Laboratory (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)

Chemical transformations in charge transfer states result from the interplay between electronic dynamics and nuclear reorganization along excited-state trajectories. Here, in this study, we investigate the ultrafast structural dynamics following photoinduced electron transfer from the metal-metal-to-ligand charge transfer state of an electron donor, a Pt dimer complex, to a covalently linked electron acceptor group using ultrafast time-resolved wide-angle X-ray scattering and optical transient absorption spectroscopy methods to disentangle the interdependence of the excited-state electronic and nuclear dynamics. Following photoexcitation, Pt-Pt bond formation and contraction takes up to 1 ps, much slower than the corresponding process in analogous complexes without electron acceptor groups. Because the Pt-Pt distance change is slow with respect to excited-state electron transfer, it can affect the rate of electron transfer. These results have potential impacts on controlling electron transfer rates via structural alterations to the electron donor group, tuning the charge transfer driving force.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-06CH11357; AC02-76SF00515; SC0006863

OSTI ID:: 2505042

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 19 Vol. 15; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Time-resolved wide-angle X-ray scattering
coherent vibrational wavepacket
electron transfer
intersystem crossing

Title: Deciphering Charge Transfer Processes in Transition Metal Complexes from the Perspective of Ultrafast Electronic and Nuclear Motions

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