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Real-time capture of nuclear motions influencing photoinduced electron transfer
Although vibronic coupling phenomena have been recognized in the excited state dynamics of transition metal complexes, their impact on photoinduced electron transfer (PET) remains largely unexplored. This study investigates coherent wavepacket (CWP) dynamics during PET processes in a covalently linked electron donor–acceptor complex featuring a cyclometalated Pt(II) dimer as the donor and naphthalene diimide (NDI) as the acceptors. Upon photoexciting the Pt(II) dimer electron donor, ultrafast broadband transient absorption spectroscopy revealed direct modulation of NDI radical anion formation through certain CWP motions and correlated temporal evolutions of the amplitudes for these CWPs with the NDI radical anion formation. These results provide clear evidence that the CWP motions are the vibronic coherences coupled to the PET reaction coordinates. Normal mode analysis identified that the CWP motions originate from vibrational modes associated with the dihedral angles and bond lengths between the planes of the cyclometalating ligand and the NDI, the key modes altering their p-interaction, consequently influencing PET dynamics. The findings highlight the pivotal role of vibrations in shaping the favorable trajectories for the efficient PET processes.
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- PAR ID:
- 10625317
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 15
- Issue:
- 36
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 14766 to 14777
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d4sc01876a
