The crystallisation of copper(ii) phenylphosphonates

Abstract

The crystal structures and syntheses of four different copper(ii) phenylphosphonates, the monophenylphosphonates α-, β-, and γ-Cu(OPCH)·HO (α-CuPhPmH (1) β-CuPhPmH (2) and γ-CuPhPmH (3)), and the diphosphonate Cu(HOPCH)·HO (CuPhP2mH (4)), are presented. The compounds were synthesized from solution at room temperature, at elevated temperature, under hydrothermal conditions, and mechanochemical conditions. The structures of α-CuPhPmH (1) and CuPhP2mH (4) were solved from powder X-ray diffraction data. The structure of β-CuPhPmH (2) was solved by single crystal X-ray analysis. The structures were validated by extended X-ray absorption fine structure (EXAFS) and DTA analyses. Disorder of the crystal structure was elucidated by electron diffraction. The relationship between the compounds and their reaction pathways were investigated by in situ synchrotron measurements.

Hybrid Organic–Inorganic Transition‐Metal Phosphonates as Precursors for Water Oxidation Electrocatalysts

“…The average interlayer distances calculated from the (010) reflections are 1.53 ± 0.05 nm, and match well the values measured by TEM. The interlayer spacing in this type of structures is determined by the size of the organic ligand . It is worth mentioning that the reflections in the XRD pattern of NiFe0 are broader than those of a Ni‐phenylphosphonate compound reported in a previous work, which was synthesized from a more concentrated reaction mixture .…”

“…The coordination structure of the resulting hybrid will depend on the metal, synthesis conditions, and presence of additional coordinating moieties including those in the organic part of the phosphonate ligand (e.g., carboxylate, sulfonate, pyridine, hydroxyl, or phosphonate). The versatility of the coordination chemistry of phosphonates leads to a variety of possible local coordination environments around the metal centers, a feature that is attractive for tuning the electrocatalytic metal sites . However, this family of hybrid materials remains almost unexplored as water oxidation catalysts, as only a few promising reports are available in the literature concerning the application of cobalt phosphonates as photocatalytic water oxidation catalysts .…”

3D Electron Diffraction: The Nanocrystallography Revolution

“…NED gives full control on the beam diameter used and in principle also allows collecting data on a smaller area with respect to SAED. Consequently it is the method of choice in the case of low crystallinity, high mosaicity, or order–disorder polytypism at the nanoscale. ,,,,− …”

Structure analysis of materials at the order–disorder borderline using three-dimensional electron diffraction

“…A peculiar combination of stacking disorder and twinning was found in nanocrystalline metal-organic phenylphosphonates (Wilke et al, 2016). The layered structure consisted of rigid inorganic layers decorated from both sides with phenyl groups.…”

“…However, minerals and inorganic materials are not the only materials that may benefit from OD interpretation. Stacking disorder is indeed quite frequent in organic and metal-organic materials Wilke et al, 2016), and may be interpreted and described by the OD theory (Teteruk et al, 2014).…”