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Triplet Excited State Distortions in a Pyrazolate Bridged Platinum Dimer Measured by X-ray Transient Absorption Spectroscopy.

Lockard, Jenny V; Rachford, Aaron A; Smolentsev, Grigory LU ; Stickrath, Andrew B; Wang, Xianghuai; Zhang, Xiaoyi; Atenkoffer, Klaus; Jennings, Guy; Soldatov, Alexander and Rheingold, Arnold L, et al. (2010) In Journal of physical chemistry. A 114(48). p.12780-12787
Abstract
The excited-state structure of a dinuclear platinum(II) complex with tert-butyl substituted pyrazolate bridging units, [Pt(ppy)(μ-(t)Bu(2)pz)](2) (ppy = 2-phenylpyridine; (t)Bu(2)pz = 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... (More)
The excited-state structure of a dinuclear platinum(II) complex with tert-butyl substituted pyrazolate bridging units, [Pt(ppy)(μ-(t)Bu(2)pz)](2) (ppy = 2-phenylpyridine; (t)Bu(2)pz = 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. (Less)
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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of physical chemistry. A
volume
114
issue
48
pages
12780 - 12787
publisher
The American Chemical Society
external identifiers
  • wos:000284738500028
  • pmid:21067164
  • scopus:78649875460
ISSN
1520-5215
DOI
10.1021/jp1088299
language
English
LU publication?
yes
id
6120453b-06c5-4749-b9ae-56df1f362bf6 (old id 1732094)
date added to LUP
2010-12-15 12:44:50
date last changed
2018-07-15 03:42:40
@article{6120453b-06c5-4749-b9ae-56df1f362bf6,
  abstract     = {The excited-state structure of a dinuclear platinum(II) complex with tert-butyl substituted pyrazolate bridging units, [Pt(ppy)(μ-(t)Bu(2)pz)](2) (ppy = 2-phenylpyridine; (t)Bu(2)pz = 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.},
  author       = {Lockard, Jenny V and Rachford, Aaron A and Smolentsev, Grigory and Stickrath, Andrew B and Wang, Xianghuai and Zhang, Xiaoyi and Atenkoffer, Klaus and Jennings, Guy and Soldatov, Alexander and Rheingold, Arnold L and Castellano, Felix N and Chen, Lin X},
  issn         = {1520-5215},
  language     = {eng},
  number       = {48},
  pages        = {12780--12787},
  publisher    = {The American Chemical Society},
  series       = {Journal of physical chemistry. A},
  title        = {Triplet Excited State Distortions in a Pyrazolate Bridged Platinum Dimer Measured by X-ray Transient Absorption Spectroscopy.},
  url          = {http://dx.doi.org/10.1021/jp1088299},
  volume       = {114},
  year         = {2010},
}