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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 (ACS)
external identifiers
  • wos:000284738500028
  • pmid:21067164
  • scopus:78649875460
  • pmid:21067164
ISSN
1520-5215
DOI
10.1021/jp1088299
language
English
LU publication?
yes
additional info
The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)
id
6120453b-06c5-4749-b9ae-56df1f362bf6 (old id 1732094)
date added to LUP
2016-04-01 13:05:19
date last changed
2023-11-12 11:48:38
@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 (ACS)}},
  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}},
  doi          = {{10.1021/jp1088299}},
  volume       = {{114}},
  year         = {{2010}},
}