Triplet Excited State Distortions in a Pyrazolate Bridged Platinum Dimer Measured by X-ray Transient Absorption Spectroscopy.
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/1732094
- author
- organization
- publishing date
- 2010
- 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}}, }