A rare Mn9 micro3-oxo-centered mixed-valent cluster [Mn9O7(O2CPh)11(thmn)(py)2 (H2O)3] (1) is prepared by assembling an oxo-centered MnIIMnIII2 triangle, [Mn3O(O2CPh)6(py)2(H2O)].0.5MeCN, as the secondary building unit in the presence of a tripodal alcohol, 1,1,1-tris(hydroxymethyl)nitromethane (H3thmn), as the capping ligand. Complex 1 was formed along with a minor byproduct, [Mn6O2(O2CPh)10(MeCN)4] (2). Complex 1 was characterized by X-ray single-crystal structure analysis and was crystallized in a monoclinic system, space group P2(1)/n, a=16.214(6) A, b=25.874(10) A, c=26.497(10) A, and beta=94.214(7) degrees. The Manganese-oxo-carboxylate core in 1 looks like a funnel. Variable-temperature magnetic studies down to 2 K reveal the existence of dominant ferromagnetic interaction within the cluster. Alternating current susceptibility data of the cluster show strong frequency dependence of both the real and imaginary parts of susceptibility chi' and chi'' below 5 K. Moreover, the calculated relaxation time, tau0=1.2x10(-7) s, and the energy barrier, DeltaE=25 K, are consistent with the single-molecule magnetic behavior of 1.
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Front Chem
December 2024
School of Energy and Power Engineering, Xi'an Jiaotong University, Xi'an, China.
Studies on cerium oxo clusters (CeOCs) are not only significant for understanding the redox and hydrolysis behaviors of Ce(III/IV) ions but also crucial for the rational synthesis of novel clusters and nanoceria with specific Ce(III)/Ce(IV) ratios. Here, two sets of reactions were conducted using cerium nitrate and HO-oxidized cerium nitrate, resulting in the formation of two distinct mixed-valent CeOCs [Ce Ce O(OH)(PhCO)(DMF)] (Ce) and [Ce Ce O(OH)(PhCO)(DMF)] (Ce). These two clusters exhibit different structures and Ce(III)/Ce(IV) ratios, demonstrating the critical role of cerium oxidation states and the occurrence of redox reactions in cluster formation.
View Article and Find Full Text PDFFront Chem
October 2024
EaStCHEM School of Chemistry, The University of Edinburgh, Edinburgh, Scotland, United Kingdom.
The reaction of MnCl·4HO with HL ((1-methyl-1H-imidazol-2-yl)methanol) and pdH (1, 3 propanediol) in a basic MeCN solution results in the formation of a mixed-valence [Mn] cationic cluster and two [MnCl] counter anions. The metallic skeleton of the cluster describes two geometrically equivalent mixed-valent, linked [Mn Mn ] supertetrahedra in which nearest-neighbor metal ions have a different oxidation state. Magnetic susceptibility, magnetization data and heat capacity measurements support evidence of predominant ferromagnetic correlations, leading to a = 22 spin ground state for the [Mn Mn ] supertetrahedra, which are pair-linked by a weak antiferromagnetic coupling.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Department of Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128, Mainz, Germany.
Polyoxometalates (POMs) are ideal components for reversible multi-electron storage in energy technologies. To-date, most redox-applications employ only single, individual POM species, which limits the number of electrons that can be stored within a given potential window. Here, we report that spontaneous redox self-equilibration during cluster synthesis leads to the formation of two structurally related polyoxovanadates which subsequently aggregate into co-crystals.
View Article and Find Full Text PDFChem Commun (Camb)
August 2024
Fujian Provincial Key Laboratory of Advanced Inorganic Oxygenated-Materials, College of Chemistry, Fuzhou University, Fuzhou, Fujian 350108, China.
A rare all-inorganic high-nuclearity mixed-valent {Mn} cluster embedded polyoxoniobate, KH{(TeNbO)(NbO)(TeNbO)[(TeO)(MnII7MnIII4O)]}·97HO (1), has been synthesized by a one-pot reaction. Compound 1 contains the largest manganese cluster {Mn} core among polyoxoniobates reported to date. {Mn} consists of three quasi-cubane {MnO} units and is simultaneously encapsulated by lacunary α-Keggin {TeNbO} and Lindqvist {NbO} units.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Department of Electrical Engineering and Information Systems, The University of Tokyo, 7-3-1 Bunkyo-ku, Tokyo, 113-8656, Japan.
Polyoxometalates (POMs) are nanosized molecular metal oxide anion clusters with tuneable structures and functionalities, and they exhibit a redox chemistry and catalytic activity in multielectron redox processes. These are typically poor electrical conductors (<10 Scm), which is attributed to negligible electronic interactions among anions in the solid state. Since the reduced electrons on the d metals in POMs are delocalized, electrical conductivity was improved when judicious pathways for the electrons were created by bridging the POMs.
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