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Structure and ultrafast dynamics of tri-nuclear Ag-/Tl-Pt2POP4 complexes in solution

Lenzen, Philipp ; Haldrup, Kristoffer ; Dohn, Asmus O. ; Beyer, Frederik ; Biasin, Elisa ; Christensen, Morten ; Hansen, Bianca L. ; Harlang, Tobias LU ; Kjær, Kasper Skov LU and Laursen, Mads Goldschmidt , et al. (2025) In Structural Dynamics 12(4).
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 [Pt2(H2P2O5) 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... (More)

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 [Pt2(H2P2O5) 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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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Structural Dynamics
volume
12
issue
4
article number
044902
publisher
AAPM - American Association of Physicists in Medicine
external identifiers
  • pmid:40666623
  • scopus:105010656864
ISSN
2329-7778
DOI
10.1063/4.0000293
language
English
LU publication?
yes
additional info
Publisher Copyright: © 2025 Author(s).
id
457153a7-86f5-4d73-b1e4-9c734f46b364
date added to LUP
2025-12-22 11:46:33
date last changed
2025-12-23 03:00:09
@article{457153a7-86f5-4d73-b1e4-9c734f46b364,
  abstract     = {{<p>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<sub>2</sub>(H<sub>2</sub>P<sub>2</sub>O<sub>5</sub>) 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 &lt;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.</p>}},
  author       = {{Lenzen, Philipp and Haldrup, Kristoffer and Dohn, Asmus O. and Beyer, Frederik and Biasin, Elisa and Christensen, Morten and Hansen, Bianca L. and Harlang, Tobias and Kjær, Kasper Skov and Laursen, Mads Goldschmidt and Vester, Peter and van Driel, Tim B. and Chollet, Matthieu and Glownia, James M. and Hartsock, Robert J. and Lemke, Henrik T. and Nelson, Silke and Song, Sanghoon and Pedersen, Kasper Steen and Gaffney, Kelly J. and Møller, Klaus B. and Nielsen, Martin M.}},
  issn         = {{2329-7778}},
  language     = {{eng}},
  month        = {{05}},
  number       = {{4}},
  publisher    = {{AAPM - American Association of Physicists in Medicine}},
  series       = {{Structural Dynamics}},
  title        = {{Structure and ultrafast dynamics of tri-nuclear Ag-/Tl-Pt<sub>2</sub>POP<sub>4</sub> complexes in solution}},
  url          = {{http://dx.doi.org/10.1063/4.0000293}},
  doi          = {{10.1063/4.0000293}},
  volume       = {{12}},
  year         = {{2025}},
}