DOE OSTI · 2587702
Structure and ultrafast dynamics of tri-nuclear Ag-/Tl–Pt 2 POP 4 complexes in solution
Abstract
The energetics and dynamics of ion assembly in solution has broad influence in nanomaterials and inorganic synthesis. To investigate the fundamental processes involved, we present a time-resolved x-ray solution scattering (TR-XSS) study of the trinuclear silver and thallium complexes of the diplatinum ion PtPOP [Pt 2 (H 2 P 2 O 5 )$_4^{4−}$] in aqueous solution. These complexes, their structural properties, and their electronic structure are not well understood and afford a unique opportunity to study the metal–metal bond formation that influences molecular and material assembly in solution. We present model-independent analysis of the observed dynamics as well as an analysis incorporating time-resolved structural refinements of key bond lengths with $<$100 fs time resolution. We find that upon photoexcitation, the Pt atoms contract ∼0.25 Å toward the center of both the Ag- and the Tl-PtPOP complexes, as previously observed for the PtPOP anion. For the AgPtPOP system, an ultrafast Ag-Pt bond expansion of ∼0.2 Å is observed, whereas in contrast, the TlPtPOP system exhibits a Tl-Pt bond contraction of ∼0.3 Å upon photoexcitation. For both complexes, the change in electronic state leads to coherent (“wave-packet”) oscillations along the metal–Pt coordinates. Based on these structural dynamics, we propose an electronic structure model that describes the metal–metal bonding behavior in both the ground and excited state for both complexes.
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Lenzen, Philipp [Technical Univ. of Denmark, Lyngby (Denmark)], Haldrup, Kristoffer [Technical Univ. of Denmark, Lyngby (Denmark)] (ORCID:0000000205656397), Dohn, Asmus O. [Technical Univ. of Denmark, Lyngby (Denmark); Univ. of Iceland, Reykjavík (Iceland)] (ORCID:0000000251727168), Beyer, Frederik [Technical Univ. of Denmark, Lyngby (Denmark)] (ORCID:0009000366860628), Biasin, Elisa [Technical Univ. of Denmark, Lyngby (Denmark); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Institute (PULSE)] (ORCID:0000000272764224), Christensen, Morten [Technical Univ. of Denmark, Lyngby (Denmark)], Hansen, Bianca L. [Technical Univ. of Denmark, Lyngby (Denmark)] (ORCID:000000024279780X), Harlang, Tobias [Technical Univ. of Denmark, Lyngby (Denmark); Lund Univ. (Sweden)] (ORCID:0000000220566883), Kjær, Kasper Skov [Technical Univ. of Denmark, Lyngby (Denmark); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Institute (PULSE); Lund Univ. (Sweden)], Laursen, Mads Goldschmidt [Technical Univ. of Denmark, Lyngby (Denmark)] (ORCID:0000000153144612), Vester, Peter [Technical Univ. of Denmark, Lyngby (Denmark)] (ORCID:0000000297067126), van Driel, Tim B. [Technical Univ. of Denmark, Lyngby (Denmark); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)] (ORCID:0000000340703168), Chollet, Matthieu [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)] (ORCID:000000029629890X), Glownia, James M. [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)], Hartsock, Robert J. [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Institute (PULSE)], Lemke, Henrik T. [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Linac Coherent Light Source (LCLS); Paul Scherrer Inst. (PSI), Villigen (Switzerland)] (ORCID:0000000315778643), Nelson, Silke [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)], Song, Sanghoon [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)] (ORCID:0000000334931850), Pedersen, Kasper Steen [Technical Univ. of Denmark, Lyngby (Denmark)] (ORCID:0000000243814544), Gaffney, Kelly J. [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Institute (PULSE)] (ORCID:0000000205256465), Møller, Klaus B. [Technical Univ. of Denmark, Lyngby (Denmark)] (ORCID:0000000297977437), Nielsen, Martin M. [Technical Univ. of Denmark, Lyngby (Denmark)] (ORCID:000000028135434X). 2025-07-10. Structure and ultrafast dynamics of tri-nuclear Ag-/Tl–Pt 2 POP 4 complexes in solution. https://doi.org/10.1063/4.0000293
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