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Retrieving photochemically active structures by time-resolved EXAFS spectroscopy

Renske M van der Veen1,2, Christian Bressler1,2,3, Chris J Milne1, Van-Thai Pham1, Amal El Nahhas1, Frederico A Lima1, Wojciech Gawelda1,4, Camelia N Borca2, Rafael Abela2 and Majed Chergui1

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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(P2O5H2)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) Å of the two Pt atoms and a ligand expansion of 0.010(6) Å. 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.


PACS

82.50.-m Photochemistry

61.25.Em Molecular liquids

82.65.+r Surface and interface chemistry; heterogeneous catalysis at surfaces

71.20.Rv Polymers and organic compounds

78.70.Dm X-ray absorption spectra

Subjects

Soft matter, liquids and polymers

Condensed matter: electrical, magnetic and optical

Surfaces, interfaces and thin films

Chemical physics and physical chemistry

Dates

Issue 1 (2009)



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