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Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy

Hayes, Dugan and Kohler, Lars and Hadt, Ryan G. and Zhang, Xiaoyi and Liu, Cunming and Mulfort, Karen L. and Chen, Lin X. (2018) Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy. Chemical Science, 9 (4). pp. 860-875. ISSN 2041-6520 . PMCID PMC5873173. http://resolver.caltech.edu/CaltechAUTHORS:20180612-093858300

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Abstract

The kinetics of photoinduced electron and energy transfer in a family of tetrapyridophenazine-bridged heteroleptic homo- and heterodinuclear copper(I) bis(phenanthroline)/ruthenium(II) polypyridyl complexes were studied using ultrafast optical and multi-edge X-ray transient absorption spectroscopies. This work combines the synthesis of heterodinuclear Cu(I)–Ru(II) analogs of the homodinuclear Cu(I)–Cu(I) targets with spectroscopic analysis and electronic structure calculations to first disentangle the dynamics at individual metal sites by taking advantage of the element and site specificity of X-ray absorption and theoretical methods. The excited state dynamical models developed for the heterodinuclear complexes are then applied to model the more challenging homodinuclear complexes. These results suggest that both intermetallic charge and energy transfer can be observed in an asymmetric dinuclear copper complex in which the ground state redox potentials of the copper sites are offset by only 310 meV. We also demonstrate the ability of several of these complexes to effectively and unidirectionally shuttle energy between different metal centers, a property that could be of great use in the design of broadly absorbing and multifunctional multimetallic photocatalysts. This work provides an important step toward developing both a fundamental conceptual picture and a practical experimental handle with which synthetic chemists, spectroscopists, and theoreticians may collaborate to engineer cheap and efficient photocatalytic materials capable of performing coulombically demanding chemical transformations.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1039/C7SC04055EDOIArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5873173/PubMed CentralArticle
ORCID:
AuthorORCID
Hayes, Dugan0000-0003-4171-5179
Hadt, Ryan G.0000-0001-6026-1358
Zhang, Xiaoyi0000-0001-9732-1449
Liu, Cunming0000-0002-1733-7991
Mulfort, Karen L.0000-0002-3132-1179
Chen, Lin X.0000-0002-8450-6687
Additional Information:© 2018 The Author(s). This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Received 15th September 2017, Accepted 14th November 2017. First published on 28th November 2017. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, through Argonne National Laboratory (ANL) under Contract No. DE-AC02-06CH11357. D. H. acknowledges support from the Joseph J. Katz Fellowship from ANL, and R. G. H. acknowledges support from the Enrico Fermi Fellowship from ANL. Use of the Advanced Photon Source (APS) at ANL is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-06CH11357. We thank Dr Richard E. Wilson (ANL) for assistance in collecting the X-ray diffraction data and Dr Matthias Zeller (Purdue University) for assistance in solving the crystal structure. We gratefully acknowledge the computing resources provided on Blues and Fusion, a high-performance computing cluster operated by the Laboratory Computing Resource Center at ANL. There are no conflicts of interest to declare.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-AC02-06CH11357
Argonne National LaboratoryUNSPECIFIED
PubMed Central ID:PMC5873173
Record Number:CaltechAUTHORS:20180612-093858300
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180612-093858300
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86995
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:12 Jun 2018 17:09
Last Modified:12 Jun 2018 17:09

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