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Retrieving photochemically active structures by time-resolved EXAFS spectroscopy

Van Der Veen, Renske M. ; Bressler, Christian ; Milne, Chris J. ; Nahhas, Amal El LU ; Lima, Frederico A. ; Gawelda, Wojciech ; Borca, Camelia N. ; Abela, Rafael ; Chergui, Majed and Pham, Van-Thai LU (2009) In Journal of Physics: Conference Series 190(1).
Abstract

Describing the nature and structure of molecular excited states is important in order to understand their chemical reactivity and role as intermediates in photochemical reactions. The recent implementation of X-ray absorption spectroscopy in the ultrafast time domain allows studying the electronic and structural dynamics of photochemically active molecules in solutions. In this work we present the structural determination of a photoexcited diplatinum molecule, [Pt2(P2O 5H2)4]4-, which plays a photocatalytic role in important chemical conversions. A novel analysis of time-resolved EXAFS spectra based on the fitting of the experimental transients obtained from optical... (More)

Describing the nature and structure of molecular excited states is important in order to understand their chemical reactivity and role as intermediates in photochemical reactions. The recent implementation of X-ray absorption spectroscopy in the ultrafast time domain allows studying the electronic and structural dynamics of photochemically active molecules in solutions. In this work we present the structural determination of a photoexcited diplatinum molecule, [Pt2(P2O 5H2)4]4-, which plays a photocatalytic role in important chemical conversions. A novel analysis of time-resolved EXAFS spectra based on the fitting of the experimental transients obtained from optical pump/x-ray probe experiments has been performed to derive a contraction of 0.31(5) of the two Pt atoms and a ligand expansion of 0.010(6) . The former is assigned to the formation of a transient Pt-Pt bond in the excited state, while the latter indicates a concomitant weakening of the Pt-ligand coordination bonds.

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publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Physics: Conference Series
volume
190
issue
1
article number
012054
publisher
IOP Publishing
external identifiers
  • scopus:73449126890
ISSN
1742-6588
DOI
10.1088/1742-6596/190/1/012054
language
English
LU publication?
no
id
97a86310-fa19-4faf-b7bd-8b6be9592110
date added to LUP
2019-06-30 09:58:27
date last changed
2020-04-02 02:36:36
@article{97a86310-fa19-4faf-b7bd-8b6be9592110,
  abstract     = {<p>Describing the nature and structure of molecular excited states is important in order to understand their chemical reactivity and role as intermediates in photochemical reactions. The recent implementation of X-ray absorption spectroscopy in the ultrafast time domain allows studying the electronic and structural dynamics of photochemically active molecules in solutions. In this work we present the structural determination of a photoexcited diplatinum molecule, [Pt<sub>2</sub>(P<sub>2</sub>O <sub>5</sub>H<sub>2</sub>)<sub>4</sub>]<sup>4-</sup>, which plays a photocatalytic role in important chemical conversions. A novel analysis of time-resolved EXAFS spectra based on the fitting of the experimental transients obtained from optical pump/x-ray probe experiments has been performed to derive a contraction of 0.31(5) of the two Pt atoms and a ligand expansion of 0.010(6) . The former is assigned to the formation of a transient Pt-Pt bond in the excited state, while the latter indicates a concomitant weakening of the Pt-ligand coordination bonds.</p>},
  author       = {Van Der Veen, Renske M. and Bressler, Christian and Milne, Chris J. and Nahhas, Amal El and Lima, Frederico A. and Gawelda, Wojciech and Borca, Camelia N. and Abela, Rafael and Chergui, Majed and Pham, Van-Thai},
  issn         = {1742-6588},
  language     = {eng},
  month        = {01},
  number       = {1},
  publisher    = {IOP Publishing},
  series       = {Journal of Physics: Conference Series},
  title        = {Retrieving photochemically active structures by time-resolved EXAFS spectroscopy},
  url          = {http://dx.doi.org/10.1088/1742-6596/190/1/012054},
  doi          = {10.1088/1742-6596/190/1/012054},
  volume       = {190},
  year         = {2009},
}