General Design Rules for Bimetallic Platinum(II) ComplexesClick to copy article linkArticle link copied!
- Alexis W. MillsAlexis W. MillsDepartment of Chemistry, University of Washington, Seattle, Washington 98195, United StatesMore by Alexis W. Mills
- Andrew J. S. ValentineAndrew J. S. ValentineDepartment of Chemistry, University of Washington, Seattle, Washington 98195, United StatesMore by Andrew J. S. Valentine
- Kevin HoangKevin HoangDepartment of Chemistry, University of Washington, Seattle, Washington 98195, United StatesMore by Kevin Hoang
- Subhangi RoySubhangi RoyDepartment of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, United StatesMore by Subhangi Roy
- Felix N. CastellanoFelix N. CastellanoDepartment of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, United StatesMore by Felix N. Castellano
- Lin X. ChenLin X. ChenChemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United StatesDepartment of Chemistry, Northwestern University, Evanston, Illinois 60208, United StatesMore by Lin X. Chen
- Xiaosong Li*Xiaosong Li*Email: [email protected]Department of Chemistry, University of Washington, Seattle, Washington 98195, United StatesMore by Xiaosong Li
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.
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