Exploiting the Multifunctionality of M/Imidazole-Etidronates for Proton Conductivity (Zn) and Electrocatalysis (Co, Ni) toward the HER, OER, and ORR.

This work deals with the synthesis and characterization of one-dimensional (1D) imidazole-containing etidronates, [M(ETID)(Im)]·HO (M = Co and Ni; = 0, 1, 3) and [Zn(ETID)(HO)](Im), as well as the corresponding Co/Ni solid solutions, to evaluate their properties as multipurpose materials for energy conversion processes. Depending on the water content, metal ions in the isostructural Co and Ni derivatives are octahedrally coordinated ( = 3) or consist of octahedral together with dimeric trigonal bipyramidal ( = 1) or square pyramidal ( = 0) environments. The imidazole molecule acts as a ligand (Co, Ni derivatives) or charge-compensating protonated species (Zn derivative).

Phosphonate Decomposition-Induced Polyoxomolybdate Dumbbell-Type Cluster Formation: Structural Analysis, Proton Conduction, and Catalytic Sulfoxide Reduction.

The reaction of MoO with a number of phosphonic acids [bis(phosphonomethyl)glycine, -hydroxyphosphonoacetic acid, 1-hydroxyethane-1,1-diphosphonic acid, phenylphosphonic acid, aminotris(methylene phosphonic acid), and 1,2-ethylenediphosphonic acid] under oxidizing (HO) hydrothermal conditions at low pH leads to rupture of the P-C bond, release of orthophosphate ions, and generation of the octanuclear, phosphate-bridged, polyoxometalate molybdenum cluster (NH)[Mo(OH)O(μ-PO)](HO) (). This cluster has been fully characterized and its structure determined. It was studied as a proton conductor, giving moderate values of σ = 2.

Three-Component Copper-Phosphonate-Auxiliary Ligand Systems: Proton Conductors and Efficient Catalysts in Mild Oxidative Functionalization of Cycloalkanes.

The synthesis, structural characterization, topological analysis, proton conductivity, and catalytic properties are reported of two Cu(II)-based compounds, namely a dinuclear Cu(II) complex [Cu(μ-VPA)(phen)(HO)]·8HO (1) (HVPA = vinylphosphonic acid, phen = 1,10-phenanthroline) and a 1D coordination polymer [Cu(μ-SO)(phen)(HO)] (2). Their structural features and H-bonding interactions were investigated in detail, showing that the metal-organic structures of 1 and 2 are extended by multiple hydrogen bonds to more complex 2D or 1D H-bonded architectures with the kgd [Shubnikov plane net (3.6.