Journal ArticleDOI
Inorganic Electron Transfer: Sharpening a Fuzzy Border in Mixed Valency and Extending Mixed Valency across Supramolecular Systems
TLDR
The first experiments to observe and analyze the coalescence of ν(CO) band shapes in the 1D IR spectra of mixed-valence complexes of the type {[Ru3O(OAc)6(CO)(L)]2-BL}(-), to estimate rate constants of intramolecular electron transfer (ET).Abstract:
This article describes research from our laboratory on the chemistry and spectroscopic properties of inorganic mixed-valence complexes. After a brief review of the seminal work of Taube, Creutz, Day, Robin, Hush, and others in the 1960s and the confounding efforts to identify the borderline between class II and III mixed-valence systems in the 1990s and early 2000s, we describe our first experiments to observe and analyze the coalescence of ν(CO) band shapes in the 1D IR spectra of mixed-valence complexes of the type {[Ru3O(OAc)6(CO)(L)]2-BL}−, where L = a pyridyl ligand and BL = pyrazine or 4,4′-bipyridine, to estimate rate constants of intramolecular electron transfer (ET). The strong involvement of the bridging ligands in mixed-valence complexes of this type was first identified in the appearance of totally symmetric vibrational modes of pyrazine bridging ligands in the IR because of strong vibronic coupling within a three-state metal cluster–bridge–metal cluster model. Application of the Brunschwig–Cr...read more
Citations
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Developing a Mechanistic Understanding of Molecular Electrocatalysts for CO2 Reduction using Infrared Spectroelectrochemistry
TL;DR: The use of infrared spectroelectrochemistry (IR-SEC) as a characterization method for molecular electrocatalysts allows researchers to identify key intermediates and products during the course of an electrochemical reaction.
Journal ArticleDOI
FTIR studies of metal ligands, networks of hydrogen bonds, and water molecules near the active site Mn4CaO5 cluster in Photosystem II
TL;DR: Knowing the influence of specific residues on the water molecules that serve as substrate or as participants in the networks of hydrogen bonds that make up the water access and proton egress pathways will improve the understanding of water oxidation by the Mn₄CaO₅ catalyst in Photosystem II and provide insight into the design of new generations of synthetic catalysts that convert sunlight into useful forms of storable energy.
Journal ArticleDOI
In situ characterization of cofacial Co(IV) centers in Co4O4 cubane: Modeling the high-valent active site in oxygen-evolving catalysts
Casey N. Brodsky,Ryan G. Hadt,Dugan Hayes,Benjamin Reinhart,Nancy Li,Lin X. Chen,Lin X. Chen,Daniel G. Nocera +7 more
TL;DR: It is demonstrated that the Co(III)2(IV)2 cubane may be electrochemically generated and the electronic properties of this unique high-valent state may be probed by in situ spectroscopy.
Journal ArticleDOI
Electronic coupling in cyclometalated ruthenium complexes
TL;DR: In this article, a review of the electronic coupling studies in mixed-valence or donor-acceptor -type complexes containing one or two cyclometalated ruthenium redox sites is presented.
Journal ArticleDOI
Influence of Anion Delocalization on Electron Transfer in a Covalent Porphyrin Donor-Perylenediimide Dimer Acceptor System
Patrick E. Hartnett,Catherine M. Mauck,Michelle A. Harris,Ryan M. Young,Yi Lin Wu,Tobin J. Marks,Michael R. Wasielewski +6 more
TL;DR: Femtosecond transient IR absorption spectroscopy provides evidence that the observed enhancement in charge separation results from electron transfer producing a delocalized PDI2 anion.
References
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Journal ArticleDOI
Electron transfers in chemistry and biology
Rudolph A. Marcus,Norman Sutin +1 more
TL;DR: In this paper, the electron transfer reactions between ions and molecules in solution have been the subject of considerable experimental study during the past three decades, including charge transfer, photoelectric emission spectra, chemiluminescent electron transfer, and electron transfer through frozen media.
Book ChapterDOI
Mixed Valence Chemistry-A Survey and Classification
Melvin B. Robin,Peter Day +1 more
TL;DR: In this article, a review is concerned with the neglected class of inorganic compounds, which contain ions of the same element in two different formal states of oxidation, and a number of references cite that many individual examples of this class have been studied, yet they have very rarely been treated as a class, and there has never before, to our knowledge, been a systematic attempt to classify their properties in terms of their electronic and molecular structures.
Journal ArticleDOI
Subpicosecond Measurements of Polar Solvation Dynamics: Coumarin 153 Revisited
TL;DR: In this article, the authors used time-resolved emission measurements of the solute coumarin 153 (C153) to probe the time dependence of solvation in 24 common solvents at room temperature.
Journal ArticleDOI
The localized-to-delocalized transition in mixed-valence chemistry.
Journal ArticleDOI
Optical transitions of symmetrical mixed-valence systems in the Class II–III transition regime
TL;DR: Spectral band shapes and intensities are calculated utilizing increasingly complex models including two to four states for borderline mixed-valence systems using free-energy surfaces constructed for harmonic diabetic surfaces and characterized as a function of increasing electronic coupling to simulate the Class II to III transition.
Related Papers (5)
Optical transitions of symmetrical mixed-valence systems in the Class II–III transition regime
Direct approach to measuring the Franck-Condon barrier to electron transfer between metal ions
Carol Creutz,Henry Taube +1 more