Abstract
A series of platinum(II) bimetallic complexes were studied to investigate the effects of ligands on both the geometric and electronic structure. Modulating the Pt-Pt distance through the bridging ligand architecture was found to dictate the nature of the lowest energy electronic transitions, localized in one-half of the molecule or delocalized across the entire molecule. By reducing the separation between the platinum atoms, the lowest energy electronic transitions will be dominated by the metal-metal-to-ligand charge transfer transition. Conversely, by increasing the distance between the platinum atoms, the lowest electronic transition will be largely localized metal-to-ligand charge transfer or ligand centered in nature. Additionally, the cyclometalating ligands were observed to have a noticeable stabilizing effect on the triplet excited states as the conjugation increased, arising from geometric reorientation and increased electron delocalization of the ligands. Such stabilization of the triplet state energy has been shown to alter the excited state potential energy landscape as well as the excited state trajectory.
Original language | English (US) |
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Pages (from-to) | 9438-9449 |
Number of pages | 12 |
Journal | Journal of Physical Chemistry A |
Volume | 125 |
Issue number | 43 |
DOIs | |
State | Published - Nov 4 2021 |
Funding
This work was supported 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 No. DE-AC02-06CH11357. The development of time-dependent electronic structure methods is supported by the National Science Foundation (CHE-1856210 to X.L.). Computations were facilitated through the use of advanced computational, storage, and networking infrastructure provided by the Hyak supercomputer system at the University of Washington, funded by the Student Technology Fee. L.X.C. is grateful for the support from the National Science Foundation (CHE-1955806). F.N.C. was supported by the National Science Foundation (CHE-1955795).
ASJC Scopus subject areas
- Physical and Theoretical Chemistry