Triplet excited state distortions in a pyrazolate bridged platinum dimer measured by X-ray transient absorption spectroscopy

Jenny V. Lockard; Aaron A. Rachford; Grigory Smolentsev; Andrew B. Stickrath; Xianghuai Wang; Xiaoyi Zhang; Klaus Atenkoffer; Guy Jennings; Alexander Soldatov; Arnold L. Rheingold; Felix N. Castellano; Lin X. Chen

doi:10.1021/jp1088299

Triplet excited state distortions in a pyrazolate bridged platinum dimer measured by X-ray transient absorption spectroscopy

Jenny V. Lockard, Aaron A. Rachford, Grigory Smolentsev, Andrew B. Stickrath, Xianghuai Wang, Xiaoyi Zhang, Klaus Atenkoffer, Guy Jennings, Alexander Soldatov, Arnold L. Rheingold, Felix N. Castellano, Lin X. Chen

Chemistry

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69 Scopus citations

Abstract

The excited-state structure of a dinuclear platinum(II) complex with tert-butyl substituted pyrazolate bridging units, [Pt(ppy)(μ- ^tBu₂pz)]₂ (ppy = 2-phenylpyridine; ^tBu₂pz = 3,5-di-tert-butylpyrazolate) is studied by X-ray transient absorption (XTA) spectroscopy to reveal the transient electronic and nuclear geometry. DFT calculations predict that the lowest energy triplet excited state, assigned to a metal-metal-to-ligand charge transfer (MMLCT) transition, has a contraction in the Pt-Pt distance. The Pt-Pt bond length and other structural parameters extracted from fitting the experimental XTA difference spectra from full multiple scattering (FMS) and multidimensional interpolation calculations indicates a metal-metal distance decrease by approximately 0.2 Å in the triplet excited state. The advantages and challenges of this approach in resolving dynamic transient structures of nonbonding or weak-bonding dinuclear metal complexes in solution are discussed.

Original language	English (US)
Pages (from-to)	12780-12787
Number of pages	8
Journal	Journal of Physical Chemistry A
Volume	114
Issue number	48
DOIs	https://doi.org/10.1021/jp1088299
State	Published - Dec 9 2010

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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Lockard, J. V., Rachford, A. A., Smolentsev, G., Stickrath, A. B., Wang, X., Zhang, X., Atenkoffer, K., Jennings, G., Soldatov, A., Rheingold, A. L., Castellano, F. N., & Chen, L. X. (2010). Triplet excited state distortions in a pyrazolate bridged platinum dimer measured by X-ray transient absorption spectroscopy. Journal of Physical Chemistry A, 114(48), 12780-12787. https://doi.org/10.1021/jp1088299

@article{9dc3c614a8314eb2a99dfa8e1290196f,

title = "Triplet excited state distortions in a pyrazolate bridged platinum dimer measured by X-ray transient absorption spectroscopy",

abstract = "The excited-state structure of a dinuclear platinum(II) complex with tert-butyl substituted pyrazolate bridging units, [Pt(ppy)(μ- tBu2pz)]2 (ppy = 2-phenylpyridine; tBu2pz = 3,5-di-tert-butylpyrazolate) is studied by X-ray transient absorption (XTA) spectroscopy to reveal the transient electronic and nuclear geometry. DFT calculations predict that the lowest energy triplet excited state, assigned to a metal-metal-to-ligand charge transfer (MMLCT) transition, has a contraction in the Pt-Pt distance. The Pt-Pt bond length and other structural parameters extracted from fitting the experimental XTA difference spectra from full multiple scattering (FMS) and multidimensional interpolation calculations indicates a metal-metal distance decrease by approximately 0.2 {\AA} in the triplet excited state. The advantages and challenges of this approach in resolving dynamic transient structures of nonbonding or weak-bonding dinuclear metal complexes in solution are discussed.",

author = "Lockard, {Jenny V.} and Rachford, {Aaron A.} and Grigory Smolentsev and Stickrath, {Andrew B.} and Xianghuai Wang and Xiaoyi Zhang and Klaus Atenkoffer and Guy Jennings and Alexander Soldatov and Rheingold, {Arnold L.} and Castellano, {Felix N.} and Chen, {Lin X.}",

year = "2010",

month = dec,

day = "9",

doi = "10.1021/jp1088299",

language = "English (US)",

volume = "114",

pages = "12780--12787",

journal = "Journal of Physical Chemistry A",

issn = "1089-5639",

publisher = "American Chemical Society",

number = "48",

}

Lockard, JV, Rachford, AA, Smolentsev, G, Stickrath, AB, Wang, X, Zhang, X, Atenkoffer, K, Jennings, G, Soldatov, A, Rheingold, AL, Castellano, FN & Chen, LX 2010, 'Triplet excited state distortions in a pyrazolate bridged platinum dimer measured by X-ray transient absorption spectroscopy', Journal of Physical Chemistry A, vol. 114, no. 48, pp. 12780-12787. https://doi.org/10.1021/jp1088299

TY - JOUR

T1 - Triplet excited state distortions in a pyrazolate bridged platinum dimer measured by X-ray transient absorption spectroscopy

AU - Lockard, Jenny V.

AU - Rachford, Aaron A.

AU - Smolentsev, Grigory

AU - Stickrath, Andrew B.

AU - Wang, Xianghuai

AU - Zhang, Xiaoyi

AU - Atenkoffer, Klaus

AU - Jennings, Guy

AU - Soldatov, Alexander

AU - Rheingold, Arnold L.

AU - Castellano, Felix N.

AU - Chen, Lin X.

PY - 2010/12/9

Y1 - 2010/12/9

N2 - The excited-state structure of a dinuclear platinum(II) complex with tert-butyl substituted pyrazolate bridging units, [Pt(ppy)(μ- tBu2pz)]2 (ppy = 2-phenylpyridine; tBu2pz = 3,5-di-tert-butylpyrazolate) is studied by X-ray transient absorption (XTA) spectroscopy to reveal the transient electronic and nuclear geometry. DFT calculations predict that the lowest energy triplet excited state, assigned to a metal-metal-to-ligand charge transfer (MMLCT) transition, has a contraction in the Pt-Pt distance. The Pt-Pt bond length and other structural parameters extracted from fitting the experimental XTA difference spectra from full multiple scattering (FMS) and multidimensional interpolation calculations indicates a metal-metal distance decrease by approximately 0.2 Å in the triplet excited state. The advantages and challenges of this approach in resolving dynamic transient structures of nonbonding or weak-bonding dinuclear metal complexes in solution are discussed.

AB - The excited-state structure of a dinuclear platinum(II) complex with tert-butyl substituted pyrazolate bridging units, [Pt(ppy)(μ- tBu2pz)]2 (ppy = 2-phenylpyridine; tBu2pz = 3,5-di-tert-butylpyrazolate) is studied by X-ray transient absorption (XTA) spectroscopy to reveal the transient electronic and nuclear geometry. DFT calculations predict that the lowest energy triplet excited state, assigned to a metal-metal-to-ligand charge transfer (MMLCT) transition, has a contraction in the Pt-Pt distance. The Pt-Pt bond length and other structural parameters extracted from fitting the experimental XTA difference spectra from full multiple scattering (FMS) and multidimensional interpolation calculations indicates a metal-metal distance decrease by approximately 0.2 Å in the triplet excited state. The advantages and challenges of this approach in resolving dynamic transient structures of nonbonding or weak-bonding dinuclear metal complexes in solution are discussed.

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U2 - 10.1021/jp1088299

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AN - SCOPUS:78649875460

SN - 1089-5639

VL - 114

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EP - 12787

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 48

ER -

Triplet excited state distortions in a pyrazolate bridged platinum dimer measured by X-ray transient absorption spectroscopy

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