Mixed-valence (MV) systems are referred to here as MV-2 and MV-3 depending on whether two or three consecutive valence states are involved. MV-3 systems range from systems with Hubbard U>>0, corresponding to a single stable, intermediate valence state, and U<<0, corresponding to stable alternating valences differing by two units. Experiments using inelastic neutron scattering or inelastic X-ray scattering show softening of breathing phonon modes in MV systems compared with related systems with a single valence. It is hypothesized that softening is due to coupling between potential energy surfaces, corresponding to differing localizations of the electron. As predicted, softening is larger in the delocalized case. A mechanism for superconductivity is suggested.
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http://dx.doi.org/10.1098/rsta.2007.2138 | DOI Listing |
J Phys Chem Lett
January 2025
School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Thiruvananthapuram, Kerala 695551, India.
Electronic coupling between individual redox units in a molecular assembly dictates their charge transfer efficacy. Being a well-defined crystalline structure, the metal-organic framework (MOF) ensures proper positioning of redox-active moieties and provides a unique platform to unveil their charge transfer dynamics and quantification with structural relationships. Here, we demonstrate a novel redox-active MOF with near-infrared through-space intervalence charge transfer by introducing a mixed valence state inside redox-active thiazolothiazole-based ligands (DPTTZ) upon photo- or electrochemical reduction.
View Article and Find Full Text PDFInorg Chem
January 2025
Department of Chemistry, University of Southern California, Los Angeles, California 90089, United States.
The functional properties of tetraaryl compounds, M(aryl) (M = transition metal or group 14 element), are dictated not only by their common tetrahedral geometry but also by their central atom. The identity of this atom may serve to modulate the reactivity, electrochemical, magnetic, and optical behavior of the molecular species, or of extended materials built from appropriate tetraaryl building blocks, but this has not yet been systematically evaluated. Toward this goal, here we probe the influence of Os(IV), C, and Si central atoms on the spectroelectrochemical properties of a series of redox-active tetra(ferrocenylaryl) complexes.
View Article and Find Full Text PDFSci Rep
January 2025
Department of Psychology (Scarborough), University of Toronto, Toronto, ON, Canada.
Recent research has identified sex-dependent links between risk taking behaviors, approach-avoidance bias and alcohol intake. However, preclinical studies have typically assessed alcohol drinking using a singular dimension of intake (i.e.
View Article and Find Full Text PDFMikrochim Acta
January 2025
Key Laboratory of Optoelectronic Chemical Materials and Devices of Ministry of Education, College of Optoelectronic Materials and Technology, Jianghan University, Wuhan, 430056, China.
An electrochemical sensor is presented for the detection of the chloramphenicol (CAP) based on a bimetallic MIL-101(Fe/Co) MOF electrocatalyst. The MIL-101(Fe/Co) was prepared by utilizing mixed-valence Fe (III) and Co (II) as metal nodes and terephthalic acid as ligands with a simple hydrothermal method and characterized by SEM, TEM, XRD, FTIR, and XPS. Electrochemical measurements such as electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and differential pulse voltammetry (DPV) showed that bimetallic MIL-101(Fe/Co) had the faster electron transfer, larger electroactive area, and higher electrocatalytic activity compared with their monometallic counterparts due to the strong synergistic effect between bimetals.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
January 2025
Department of Chemistry, University of Kurdistan, Sanandaj 66177-15175 Iran; Research Center for Nanotechnology, University of Kurdistan, Sanandaj 66177-15175 Iran. Electronic address:
The study focuses on the synthesis of VO microcubes for the non-enzymatic colorimetric determination of HO.Vanadium oxide nanostructures are known for their redox activity and layered structures, making VO a valuable material for sensing applications. The characterization of the prepared sample was done using XPS, XRD, Raman spectroscopy, and SEM techniques.
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