Triplet Excited State Distortions in a Pyrazolate Bridged Platinum Dimer Measured by X-ray Transient Absorption Spectroscopy

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

doi:10.1021/jp1088299

Cited by 76 publications

(114 citation statements)

References 51 publications

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“…This was followed by a ps XAS study on another diplatinum comple by Chen and co-workers, 223 who also showed bond formation in the excited state with a contraction of the Pt-Pt distance by ~ 0.2 Å.…”

Section: Bond Forming Dynamicsmentioning

confidence: 87%

Photoinduced Structural Dynamics of Molecular Systems Mapped by Time-Resolved X-ray Methods

2017

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ABSTRACT:We review the tremendous advances in ultrafast X-ray science, over the past 15 years, making the best use of new ultrashort x-ray sources including table-top or large-scale facilities. Different complementary x-ray based techniques, including spectroscopy, scattering and diffraction, are presented. The broad and expanding spectrum of these techniques in the ultrafast time domain, is delivering new insight into the dynamics of molecular systems, of solutions, of solids and of Biosystems. Probing the time evolution of the electronic and structural degrees of freedom of these systems on the timescales of femtosecond to picoseconds delivers new insight into our understanding of dynamical matter.

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Section: Bond Forming Dynamicsmentioning

confidence: 87%

Photoinduced Structural Dynamics of Molecular Systems Mapped by Time-Resolved X-ray Methods

2017

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“…40 This has provided an efficient method of acquisition on a time scale of 100s ns to 1 μs with a time resolution of 100 ps. By using an optimized laser repetition rate for the SLS (520 kHz), transient XAFS of MbCO (2 mM) have been obtained in ∼4.5 h. 41 The principal disadvantage of the dispersive approach is the restriction to a transmission geometry and thus this test experiment utilized relatively high concentrations (15–20 mM).…”

Section: Discussionmentioning

confidence: 99%

Energy Dispersive XAFS: Characterization of Electronically Excited States of Copper(I) Complexes

et al. 2013

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Energy dispersive X-ray absorption spectroscopy (ED-XAS), in which the whole XAS spectrum is acquired simultaneously, has been applied to reduce the real-time for acquisition of spectra of photoinduced excited states by using a germanium microstrip detector gated around one X-ray bunch of the ESRF (100 ps). Cu K-edge XAS was used to investigate the MLCT states of [Cu(dmp)2]+ (dmp =2,9-dimethyl-1,10-phenanthroline) and [Cu(dbtmp)2]+ (dbtmp =2,9-di-n-butyl-3,4,7,8-tetramethyl-1,10-phenanthroline) with the excited states created by excitation at 450 nm (10 Hz). The decay of the longer lived complex with bulky ligands, was monitored for up to 100 ns. DFT calculations of the longer lived MLCT excited state of [Cu(dbp)2]+ (dbp =2,9-di-n-butyl-1,10-phenanthroline) with the bulkier diimine ligands, indicated that the excited state behaves as a Jahn–Teller distorted Cu(II) site, with the interligand dihedral angle changing from 83 to 60° as the tetrahedral coordination geometry flattens and a reduction in the Cu–N distance of 0.03 Å.

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“…Furthermore, TR-XAS spectroscopy has been employed to study the structural distortions in the triplet ESs of two binuclear Pt-complexes, i.e. the Pt-POP system (see also §4d) [159] and the [Pt(ppy)(µ− t Bu 2 pz)] 2 (ppy = 2-phenylpyridine; t Bu 2 pz = 3,5-di-tert-butylpyrazolate) complex [248]. Several studies concerned the structural dynamics of photodissociated intermediates in the solution phase as in the case of NiTPP-L 2 and NiTMP (where TPP = nickel tetraphenylporphyrin, L = piperidine and TMP = tetramesitylporphyrin) [249,250].…”

Section: (Py) 2 ] 2+mentioning

confidence: 99%

Synchrotron ultrafast techniques for photoactive transition metal complexes

Borfecchia

Garino

Salassa

et al. 2013

Phil. Trans. R. Soc. A.

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In the last decade, the use of time-resolved X-ray techniques has revealed the structure of lightgenerated transient species for a wide range of samples, from small organic molecules to proteins. Time resolutions of the order of 100 ps are typically reached, allowing one to monitor thermally equilibrated excited states and capture their structure as a function of time. This review aims at providing a general overview of the application of timeresolved X-ray solution scattering (TR-XSS) and time-resolved X-ray absorption spectroscopy (TR-XAS), the two techniques prevalently employed in the investigation of light-triggered structural changes of transition metal complexes. In particular, we herein describe the fundamental physical principles for static XSS and XAS and illustrate the theory of timeresolved XSS and XAS together with data acquisition and analysis strategies. Selected pioneering examples of photoactive transition metal complexes studied by TR-XSS and TR-XAS are discussed in depth.

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Triplet Excited State Distortions in a Pyrazolate Bridged Platinum Dimer Measured by X-ray Transient Absorption Spectroscopy

Cited by 76 publications

References 51 publications

Photoinduced Structural Dynamics of Molecular Systems Mapped by Time-Resolved X-ray Methods

Photoinduced Structural Dynamics of Molecular Systems Mapped by Time-Resolved X-ray Methods

Energy Dispersive XAFS: Characterization of Electronically Excited States of Copper(I) Complexes

Synchrotron ultrafast techniques for photoactive transition metal complexes

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