Butterfly deformation modes in a photoexcited pyrazolate-bridged Pt complex measured by time-resolved x-ray scattering in solution

Haldrup, Kristoffer; Dohn, Asmus O.; Shelby, Megan L.; Mara, Michael W.; Stickrath, Andrew B.; Harpham, Michael R.; Huang, Jier; Zhang, Xiaoyi; Moller, Klaus B.; Chakraborty, Arnab; Castellano, Felix N.; Tiede, David M.; Chen, Lin X.

doi:10.1021/acs.jpca.6b07728

Title: Butterfly deformation modes in a photoexcited pyrazolate-bridged Pt complex measured by time-resolved x-ray scattering in solution

Journal Article · Sat Aug 27 00:00:00 EDT 2016 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.6b07728· OSTI ID:1363790

Haldrup, Kristoffer ^[1]; Dohn, Asmus O. ^[1]; Shelby, Megan L. ^[2]; Mara, Michael W. ^[2]; Stickrath, Andrew B. ^[3]; Harpham, Michael R. ^[3]; Huang, Jier ^[3]; Zhang, Xiaoyi ^[3]; Moller, Klaus B. ^[1]; Chakraborty, Arnab ^[4]; Castellano, Felix N. ^[4]; Tiede, David M. ^[3]; Chen, Lin X. ^[5]

Technical Univ. of Denmark, Lyngby (Denmark)
Northwestern Univ., Evanston, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
North Carolina State Univ., Raleigh, NC (United States)
Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)

Pyrazolate-bridged di-nuclear Pt complexes represent a series of molecules with tunable absorption and emission properties that can be directly modulated by structural factors, such as the Pt-Pt distance. However, direct experimental information regarding the structure of the emissive triplet excited state has remained scarce. Using time-resolved wide angle X-ray scattering (WAXS), the molecular structure of the triplet excited state for one of the complexes [Pt(ppy)(μ-tBu₂pz)]₂ was obtained in a dilute (0.5 mM) toluene solution utilizing the monochromatic X-ray beamline 11IDD of the Advanced Photon Source. The excited state structural analysis was carried out based on the results from both transient WAXS measurements and DFT calculations to shed light on the primary structural changes, in particular the Pt-Pt distance and ligand rotation taking place following the photo-excitation of [Pt(ppy)(μ-tBu₂pz)]₂ in toluene solution. We find that in the triplet excited state a pronounced contraction along the Pt-Pt axis has taken place accompanied by rotational motions of ppy ligands toward one another. Our results suggest that the contraction is larger than what has previously been reported, but are in good agreement with recent theoretical efforts and suggest the ppy moieties as targets for rational synthesis aimed at tuning the excited-state structure and properties

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1363790

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 120, Issue 38; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 29 works

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