M(H2O)(PO3C10H6OH)·(H2O)0.5 (M = Co, Mn, Zn, Cu): a new series of layered metallophosphonate compounds obtained from 6-hydroxy-2-naphthylphosphonic acid

Abstract

Four new metallophosphonates M(H₂O)(PO₃C₁₀H₆OH)·(H₂O)_0.5 (M = Mn, Co, Cu, Zn) were obtained as single crystal and polycrystalline powders by hydrothermal synthesis from the precursors 6-hydroxy-2-naphthylphosphonic acid and the corresponding metal salts. These analogous hybrids crystalized in the space group P12₁/c1 in a lamellar structure. Their layered structures consisted of inorganic [M(H₂O)(PO₃C)] layers stacked with organic bilayers of 6-hydroxy-2-naphthyl moieties "HO-C₁₀H₆" and free water molecules. Their structures were determined by single crystal X-ray diffraction and confirmed by powder X-ray diffraction and Le Bail refinement for the powder sample. The removal of water upon heating at 250 °C was studied by thermogravimetric analysis and temperature-dependent powder X-ray diffraction. Their magnetic properties were studied by SQUID magnetometry and show antiferromagnetic behavior for the Co analogue and the occurrence of a canted antiferromagnetic order at T_N = 12.2 K for the Mn analogue. The Cu compound displayed an unprecedented ferromagnetic behavior. Their absorption and luminescence properties were investigated and revealed that the ligand and the compounds displayed a common behavior below a wavelength of 400 nm. Specific absorption bands were found in the compounds with Co²⁺ and Cu²⁺ at 539 nm and 849 nm, respectively. Moreover, particular luminescence bands were found for the compounds with Mn²⁺, Co²⁺ and Zn²⁺ at 598 nm, 551 nm and 530 and 611 nm, respectively.