Structural determination of a photochemically active diplatinum molecule by time-resolved EXAFS spectroscopy.

@article{Veen2009StructuralDO,
  title={Structural determination of a photochemically active diplatinum molecule by time-resolved EXAFS spectroscopy.},
  author={R. M. van der Veen and C. Milne and A. El Nahhas and F. Lima and V. Pham and Jonathan Best and J. Weinstein and C. Borca and R. Abela and C. Bressler and M. Chergui},
  journal={Angewandte Chemie},
  year={2009},
  volume={48 15},
  pages={
          2711-4
        }
}
Metallica: A large contraction of the Pt-Pt bond in the triplet excited state of the photoreactive [Pt(2)(P(2)O(5)H(2))(4)](4-) ion is determined by time-resolved X-ray absorption spectroscopy (see picture). The strengthening of the Pt-Pt interaction is accompanied by a weakening of the ligand coordination bonds, resulting in an elongation of the platinum-ligand bond that is determined for the first time. 

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References

SHOWING 1-10 OF 35 REFERENCES
Excited-state Structure of a Platinum Complex by X-ray Analysis
Irradiating a crystal of [N(C5H11)4]2[Pt2(H)2(pop)4], (pop = pyrophosphate), with a xenon lamp on a diffractometer, the intensity data were collected and the structure was analyzed by X-rays at lowExpand
Photoexcited Crystallography of Diplatinum Complex by Multiple-exposure IP Method
Molecular distortion of a photoexcited diplatinum(II) complex in a single crystal has been directly observed by accurate synchrotron radiation diffraction studies. Photoexcited crystallographicExpand
Theoretical analysis of the triplet excited state of the [Pt2(H2P2O5)4]4- ion and comparison with time-resolved X-ray and spectroscopic results.
TLDR
The ground and excited states of the [Pt(2)(pop)(4)](4-) ion are investigated using density functional theory (DFT), giving insight into the ability of the triplet excited state to abstract hydrogen and halogen atoms from organic substrates. Expand
Microsecond-resolved XAFS of the triplet excited state of Pt2(P2O5H2)4–4
TLDR
A technique that combines the X-ray absorption fine-structure (XAFS) method with rapid-flow laser spectroscopy to measure structural changes in a solution-phase excited-state transition-metal complex with microsecond resolution finds that the triplet excited state of Pt2(P2O5H2)4–4 undergoes a contraction in the Pt–Pt distance. Expand
Reexamination of the phosphorescence of Ba2Pt2(H2P2O5)4 via thermally modulated emission spectroscopy
Abstract Reexamination of the phosphorescence of Ba2Pt2(H2P2O5)4 reveals that the ≈10 K spectrum is a superposition of two electronic transitions [3A2u(Eu,A1u → A1g] separated by ≈40 cm−1. Each bandExpand
Observation of the solvent shell reorganization around photoexcited atomic solutes by picosecond X-ray absorption spectroscopy.
TLDR
Both edge spectra point to a significant rearrangement of the solvation shell around I0, suggesting a substantial amt. Expand
EXAFS structural determination of the Pt 2 (P 2 O 5 H 2 ) 4 4- anion in solution
We present the first structural detn. of the Pt2(P2O5H2)44- anion in soln. by analyzing the extended X-ray absorption fine structure (EXAFS) spectrum of the Pt LIII edge. The data could be fit with aExpand
Excited-state structure by time-resolved X-ray diffraction.
TLDR
The time-resolved diffraction technique described here is applicable to reversible light-driven processes in the crystalline solid state. Expand
Metal-metal interactions in binuclear platinum(II) diphosphite complexes. Resonance Raman spectra of the 1A1g(d.sigma.*)2 and 3A2u(d.sigma.*p.sigma.) electronic states of tetrakis(diphosphonato)diplatinate(4-) ion (Pt2(P2O5H2)44-)
Etude par resonance Raman, resolue dans le temps, du complexe du titre. Les resultats confirment que la liaison Pt-Pt dans l'etat excite 3 A 2u (d6*P6) est plus forte que dans l'etat fondamental
Binuclear platinum(II) photochemistry. Reactions of organometallic hydrides with electronically excited tetrakis(pyrophosphito)diplatinate(II)
The dsigma*Psigma triplet excited state of Pt2(P2O5H2)4U (Pt2) abstracts a hydrogen atom from R3EH (E = Sn, Ge, Si; R = alkyl, phenyl, in acetonitrile solution. The rate constant for H atom transferExpand
...
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