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Vibrational coherence transfer in the ultrafast intersystem crossing of a diplatinum complex in solution

Monni, Roberto and Capano, Gloria and Auböck, Gerald and Gray, Harry B. and Vlček, Antonín and Tavernelli, Ivano and Chergui, Majed (2018) Vibrational coherence transfer in the ultrafast intersystem crossing of a diplatinum complex in solution. Proceedings of the National Academy of Sciences of the United States of America, 115 (28). E6396-E6403. ISSN 0027-8424. PMCID PMC6048523. https://resolver.caltech.edu/CaltechAUTHORS:20180626-075430344

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Abstract

We investigate the ultrafast transient absorption response of tetrakis(μ-pyrophosphito)diplatinate(II), [Pt_2(μ-P_2O_5H_2)_4]^(4−) [hereafter abbreviated Pt(pop)], in acetonitrile upon excitation of its lowest singlet ^1A_(2u) state. Compared with previously reported solvents [van der Veen RM, Cannizzo A, van Mourik F, Vlček A, Jr, Chergui M (2011) J Am Chem Soc 133:305–315], a significant shortening of the intersystem crossing (ISC) time (<1 ps) from the lowest singlet to the lowest triplet state is found, allowing for a transfer of vibrational coherence, observed in the course of an ISC in a polyatomic molecule in solution. Density functional theory (DFT) quantum mechanical/molecular mechanical (QM/MM) simulations of Pt(pop) in acetonitrile and ethanol show that high-lying, mostly triplet, states are strongly mixed and shifted to lower energies due to interactions with the solvent, providing an intermediate state (or manifold of states) for the ISC. This suggests that the larger the solvation energies of the intermediate state(s), the shorter the ISC time. Because the latter is smaller than the pure dephasing time of the vibrational wave packet, coherence is conserved during the spin transition. These results underscore the crucial role of the solvent in directing pathways of intramolecular energy flow.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1073/pnas.1719899115DOIArticle
https://www.pnas.org/lookup/suppl/doi:10.1073/pnas.1719899115/-/DCSupplementalPublisherSupporting Information
http://www.ncbi.nlm.nih.gov/pmc/articles/pmc6048523/PubMed CentralArticle
ORCID:
AuthorORCID
Gray, Harry B.0000-0002-7937-7876
Vlček, Antonín0000-0002-6413-8311
Additional Information:© 2018 National Academy of Sciences. Published under the PNAS license. Edited by Martin Gruebele, University of Illinois at Urbana–Champaign, Urbana, IL, and approved June 1, 2018 (received for review November 23, 2017). Published ahead of print June 25, 2018. This work was supported by the Swiss National Science Foundation (NSF) via the National Center of Competence in Research/Molecular Ultrafast Science and Technology and Contract 200021_137717. We also thank the European collaboration program Cooperation in Science and Technology (Actions CM1202 and CM1405), the Czech Science Foundation (Grant 17-011375), and the NSF Center for Chemical Innovation in Solar Fuels Program (CHE-1305124) for support. Author contributions: M.C. designed research; R.M., G.C., G.A., and I.T. performed research; G.C., H.B.G., and I.T. contributed new reagents/analytic tools; R.M., G.C., G.A., A.V., I.T., and M.C. analyzed data; and M.C. wrote the paper. The authors declare no conflict of interest. This article is a PNAS Direct Submission. This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1719899115/-/DCSupplemental.
Funders:
Funding AgencyGrant Number
Swiss National Science Foundation (SNSF)200021_137717
COST ActionCM1202
COST ActionCM1405
Czech Science Foundation17-011375
NSFCHE-1305124
Subject Keywords:ultrafast; intersystem crossing; vibrational coherence; diplatinum complexes; solvation
Issue or Number:28
PubMed Central ID:PMC6048523
Record Number:CaltechAUTHORS:20180626-075430344
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180626-075430344
Official Citation:Vibrational coherence transfer in the ultrafast intersystem crossing of a diplatinum complex in solution Roberto Monni, Gloria Capano, Gerald Auböck, Harry B. Gray, Antonín Vlček, Ivano Tavernelli, Majed Chergui Proceedings of the National Academy of Sciences Jul 2018, 115 (28) E6396-E6403; DOI: 10.1073/pnas.1719899115
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:87338
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:26 Jun 2018 18:45
Last Modified:10 Apr 2020 23:32

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