A novel chain-like silver polyoxotungstophosphate is formed when Ag(I) metal centres, exhibiting an unusual eight-coordination fashion, bridge a monolacunary [PW11O39]7- anion to four bridging mu2-oxygen atoms of a neighbouring lacunary alpha-Keggin anion.
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A water-soluble mixed-valent {Mn} cluster embedded heteropolyoxoniobate with magnetic properties.
Chem 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 PDFpH-Driven Rotational Configuration of Keggin-Fe Clusters and Their Transformations.
Inorg Chem
July 2024
State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
Keggin-Fe clusters are considered foundational building blocks or prenucleation precursors of ferrihydrite. Understanding the factors that influence the rotational configuration of these clusters, and their transformations in water, is vital for comprehending the formation mechanism of ferrihydrite. Here, we report syntheses and crystal structures of four lanthanide-iron-oxo clusters, namely, [DyFe(Gly)(μ-OH)(μ-OH)(μ-O)(HO)]·13ClO·19HO (), [DyFe(Gly)(μ-OH)(μ-O)(HO)]·13ClO·14HO (), [PrFe(Gly)(μ-OH)(μ-O)(μ-O)(HO)]·6ClO·20HO (), and [PrFe(Gly)(μ-OH)(μ-O)(HO)]·13ClO·22HO (, Gly = glycine).
View Article and Find Full Text PDFCoordination of Palladium(II) and Platinum(II) Complexes to One Vacant Site in an α-Keggin-Type Polyoxotungstate.
Inorg Chem
June 2022
Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
A palladium-platinum bimetal complex containing a mono-lacunary α-Keggin-type polyoxotungstate is demonstrated. The bimetallic complex Cs{Pd(bpy)}[α-PWO{Pd(bpy)}{-Pt(NH)}]·12HO·2CHCN (bpy = 2,2'-bipyridine) () was synthesized by the reaction of CsK[α-PWO{Pt(NH)}]·10HO () with Pd(bpy)Cl in aqueous solution. The compound was characterized via elemental analysis, thermogravimetric/differential thermal analysis, and Fourier transform infrared, ultraviolet-visible, cold-spray ionization mass, and solution (H, C, and P) nuclear magnetic resonance spectroscopies.
View Article and Find Full Text PDFHerein, the geometry, electronic structure, Fe-ligand bonding nature and simulated IR spectrum of α-Keggin, lacunary Keggin, iron(ii/iii)-substituted and the important oxidized high-valent iron derivatives of Keggin type polyoxometalates have been studied using the density functional theory (DFT/OPTX-PBE) method and natural bond orbital (NBO) analysis. The effects of different Fe oxidation states (ii-vi) and HO/OH/O ligand interactions have been addressed concerning their geometry and electronic structures. It has been revealed that the d-atomic orbitals of Fe and 2p orbitals of polyoxometalate's oxygen-atoms contribute in ligand binding.
View Article and Find Full Text PDFCapturing Lacunary Iron-Oxo Keggin Clusters and Insight Into the Keggin-Fe Cluster Rotational Isomerization.
Chemistry
September 2020
Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China.
The formation mechanism of ferrihydrite is the key to understand its treatment of pollutants in waste water and purification of surface water and groundwater. Although emerging evidence suggests that formation of the ferrihydrite occurs through the aggregation of prenucleation clusters, rather than classical atom-by-atom growth, its formation mechanism remains unclear. Herein, an iron-oxo anionic cluster of [Fe (μ -O) (μ -OH) (μ -OH) (CH COO) (H O) ] viewed as a dimer of bivacant β-Keggin-Fe clusters was for the first time obtained by using lanthanide ions as stabilizers.
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