Two mixed-valence copper complexes were synthesized with ligands N-(2-pyridylmethyl)acetamide (Hpmac) and N,N'-(2-methyl-2-pyridylpropan-1,3-diyl)bis(acetamide) (H2pp(ac)2). Dimer [Cu2(pmac)2]OTf and trimer [Cu3(pp(ac)2)2].NaOTf both contain fully delocalized, mixed-valence Cu(1.5)Cu(1.5) moieties.
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http://dx.doi.org/10.1021/ic7010474 | DOI Listing |
Chemistry
December 2024
Department of Applied Chemistry, Graduate School of Engineering, Mie University, Tsu, Mie, 514-8507, Japan.
A bis(triarylamine) (BTA) radical cation, bridged by two o-terphenylene moieties, was prepared and characterized to explore the impact of the double-π-bridge on the intramolecular charge/spin transfer process in the 2-site organic mixed-valence (MV) compound. Spectroscopic analyses on optically and thermally assisted intervalence charge-transfer (IVCT) processes revealed that the doubly π-bridging enhanced the charge delocalization between two nitrogen redox-active centers, whereas the electronic coupling was not so strengthened, in comparison with the singly π-bridging reference compound.
View Article and Find Full Text PDFChem Soc Rev
December 2024
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, PO Box 14115-4838, Tehran, Islamic Republic of Iran.
Owing to increasing global demand for the development of multifunctional advanced materials with various practical applications, great attention has been paid to metal-organic frameworks due to their unique properties, such as structural, chemical, and functional diversity. Several strategies have been developed to promote the applicability of these materials in practical fields. The induction of mixed-valency is a promising strategy, contributing to exceptional features in these porous materials such as enhanced charge delocalization, conductivity, magnetism, The current review provides a detailed study of mixed-valence MOFs, including their fundamental properties, synthesis challenges, and characterization methods.
View Article and Find Full Text PDFJACS Au
November 2024
Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing 100084, China.
In this report, we present a structurally and spectroscopically characterized diorganocopper system in three distinct oxidation states: [CuCu] (), [CuCu] (), and [CuCu] (). These states are stabilized by a macrocyclic ligand scaffold featuring two square-planar coordination {C N }. We have analyzed the geometric and electronic structures using X-ray diffraction (XRD) and multiple spectroscopic methods including nuclear magnetic resonance (NMR), UV-vis, and electron paramagnetic resonance (EPR) spectroscopies, in combination with density functional theory (DFT) calculations.
View Article and Find Full Text PDFInorg Chem
December 2024
Department of Chemistry, Natural Science and Technology, Shimane University, 1060, Nishikawatsu, Matsue, Shimane 690-8504, Japan.
We have successfully synthesized unique linear-chain and discrete mixed-valence tetrameric complexes, {[Rh(3,6-DBDiox-4,5-SCO)(CO)]·hexane} () and [Rh(3,6-DBDiox-4,5-SCO)(CO)] (), by carefully choosing the solvent. X-ray photoelectron spectra (XPS) confirm that and are in the Rh(I,II) mixed-valence state. Analyses of the metrical oxidation state (MOS) of dioxolene ligands reveal that in and , the electron density corresponding to one electron per tetramer is transferred from Rh(I) ions to semiquinonato ligands, and the transferred charge is delocalized throughout the four dioxolene ligands.
View Article and Find Full Text PDFChemistry
January 2025
Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Departamento de Química Inorgánica, Analítica y Química Física, Pabellón 2, Ciudad Universitaria, C1428EHA, Buenos Aires, Argentina.
Visible-light excitation of a family of bimetallic ruthenium polypyridines with the formula [Ru(tpy)(bpy)(-CN)Ru(py)L] (RuRuL), where L=Cl, NCS, DMAP and ACN, was used to prepare photoinduced mixed-valence (PI-MV) MLCT states as models of the photosynthetic reaction center. Ultrafast transient absorption spectroscopy allowed to monitor photoinduced IVCT bands between 6000 and 11000 cm. Mulliken spin densities resulting from DFT and (TD)DFT computations revealed the modulation of the charge density distribution depending on the ligand substitution pattern.
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