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Conservation of vibrational coherence in ultrafast electronic relaxation: The case of diplatinum complexes in solution

Monni, Roberto and Auböck, Gerald and Kinschel, Dominik and Aziz-Lange, Kathrin M. and Gray, Harry B. and Vlček, Antonín and Chergui, Majed (2017) Conservation of vibrational coherence in ultrafast electronic relaxation: The case of diplatinum complexes in solution. Chemical Physics Letters, 683 . pp. 112-120. ISSN 0009-2614. doi:10.1016/j.cplett.2017.02.071.

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We report the results of ultrafast transient absorption studies of tetrakis(μ-pyrophosphito)diplatinate(II), [Pt_2(μ-P_2O_5H_2)_4]^(4−) (Pt(pop)) and its perfluoroborated derivative [Pt_2(μ-P_2O_5(BF_2)_4]^(4−) (Pt(pop-BF_2)) in water and acetonitrile upon excitation of high lying (<300 nm) UV absorption bands. We observe an ultrafast relaxation channel from high lying states to the lowest triplet state that partly (Pt(pop) in H_2O, Pt(pop-BF_2)) or fully (Pt(pop) in MeCN) bypasses the lowest singlet excited state. As a consequence, vibrational wave packets are detected in the lowest triplet state and/or the lowest excited singlet of both complexes, even though the electronic relaxation cascade spans ca. 2 and 1.3 eV, respectively. In the case of Pt(pop-BF_2), coherent wave packets generated by optical excitation of the lowest singlet ^1A_(2u) state also are reported. Overall, the reported dephasing times of the Pt-Pt oscillator in the ground, singlet and triplet states do not depend much on the solvent or the molecular structure.

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Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2017 Elsevier B.V. Received 25 January 2017, Accepted 21 February 2017, Available online 24 February 2017. This work was supported by the Swiss NSF via the NCCR:MUST, contract n° 200021_137717 and IZK0Z2_150425. We thank Yan Choi Lam and Tania Darnton for supplying samples (work at Caltech was supported by NSF CCI Solar Fuels CHE-1305124). Petr Pospíšil (J. Heyrovský Inst.) and Igor Sazanovich (Rutherford Appleton Lab, UK) are thanked for their help with measurements of stationary emission-excitation and nanosecond time-resolved spectra, respectively. We also thank the European collaboration program COST Action CM1202, the Czech Ministry of Education grant LD14129, and the Czech Science Foundation grant 17-011375 for support.
Group:CCI Solar Fuels
Funding AgencyGrant Number
Swiss National Science Foundation (SNSF)200021_137717
Swiss National Science Foundation (SNSF)IZK0Z2_150425
Ministry of Education (Czech Republic)LD14129
Czech Science Foundation17-011375
Record Number:CaltechAUTHORS:20170525-154729378
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Official Citation:Roberto Monni, Gerald Auböck, Dominik Kinschel, Kathrin M. Aziz-Lange, Harry B. Gray, Antonín Vlček, Majed Chergui, Conservation of vibrational coherence in ultrafast electronic relaxation: The case of diplatinum complexes in solution, Chemical Physics Letters, Volume 683, 2017, Pages 112-120, ISSN 0009-2614, (
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77775
Deposited By: Tony Diaz
Deposited On:25 May 2017 22:59
Last Modified:15 Nov 2021 17:33

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