Time-Resolved X-ray Scattering of an Electronically Excited State in Solution: Structure of the 3A2u State of Tetrakis-µ-pyrophosphitodiplatinate(II)
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The structure of the 3A2u excited state of tetrakis-μ-pyrophosphitodiplatinate(II) in aqueous solution is investigated by time-resolved X-ray scattering on a time scale from 100 ps to 1 μs after optical pumping. The primary structural parameter, the Pt-Pt distance, is found to be 2.74 Å, which is 0.24 Å shorter than the ground-state value. The contraction is in excellent agreement with earlier estimates based on spectroscopic data in solution and diffraction data in the crystalline state. As a second structural parameter, the distance between the P planes in the 3A2u excited state was determined to be 2.93 Å, i.e., the same as that in the ground state. This result implies that a slight lengthening of the Pt-P bond occurs following excitation.
Christensen, M., Haldrup, K., Bechgaard, K., Feidenhans'l, R., Kong, Q., Cammarata, M., Lo Russo, M., Wulff, M., Harrit, N., & Nielsen, M. M. (2009). Time-Resolved X-ray Scattering of an Electronically Excited State in Solution: Structure of the 3A2u State of Tetrakis-µ-pyrophosphitodiplatinate(II). Journal of the American Chemical Society, 131(2), 502–508. https://doi.org/10.1021/ja804485d