Triplet excited state distortions in a pyrazolate bridged platinum dimer measured by X-ray transient absorption spectroscopy

Jenny V. Lockard, Aaron A. Rachford, Grigory Smolentsev, Andrew B. Stickrath, Xianghuai Wang, Xiaoyi Zhang, Klaus Atenkoffer, Guy Jennings, Alexander Soldatov, Arnold L. Rheingold, Felix N. Castellano, Lin X. Chen

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50 Scopus citations

Abstract

The excited-state structure of a dinuclear platinum(II) complex with tert-butyl substituted pyrazolate bridging units, [Pt(ppy)(μ- tBu2pz)]2 (ppy = 2-phenylpyridine; tBu2pz = 3,5-di-tert-butylpyrazolate) is studied by X-ray transient absorption (XTA) spectroscopy to reveal the transient electronic and nuclear geometry. DFT calculations predict that the lowest energy triplet excited state, assigned to a metal-metal-to-ligand charge transfer (MMLCT) transition, has a contraction in the Pt-Pt distance. The Pt-Pt bond length and other structural parameters extracted from fitting the experimental XTA difference spectra from full multiple scattering (FMS) and multidimensional interpolation calculations indicates a metal-metal distance decrease by approximately 0.2 Å in the triplet excited state. The advantages and challenges of this approach in resolving dynamic transient structures of nonbonding or weak-bonding dinuclear metal complexes in solution are discussed.

Original languageEnglish (US)
Pages (from-to)12780-12787
Number of pages8
JournalJournal of Physical Chemistry A
Volume114
Issue number48
DOIs
StatePublished - Dec 9 2010

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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