Syntheses, Crystal Structures, Thermal Stabilities, and Magnetic and Luminescent Properties of 3D Heterometal Phosphonates: NaM[O3PCH(OH)CO2] (M = Mn, Fe, Co, Zn)

Four heterometal 2‐hydroxyl(phosphono)carboxylates,NaM[O3PCH(OH)CO2] [M = Mn (1), Fe (2), Co (3), Zn (4)], were synthesized hydrothermally. Single‐crystal X‐ray diffraction data reveal that they are isostructural and crystallize in the orthorhombic space group Pbca (No. 61) with a = 10.1365(16)–10.4557(5) Å, b = 9.6890(9)–9.8265(4) Å, c = 10.7942(19)–10.9353(1) Å, V = 1060.2(3)–1123.22(7) Å3, and Z = 8. Each [MO6] (M = Mn, Fe, Co, Zn) octahedron contacts three neighboring [NaO5] pyramids through two edges and one corner to form a Na/MO layer. The layers are further connected by O3PCH(OH)CO23– groups into an interesting 3D heterometallic framework. Thermogravimetric and powder X‐ray diffraction analysis indicate that solids 1–4 are thermally stable up to 350, 250, 340, and 350 °C, respectively. Magnetic measurements show the presence of antiferromagnetic interaction for MII ions (M = Mn, Fe, Co) in compounds 1–3. These solids exhibit bright cyan (for 1, 2, and 4) or purple (for 3) luminescence after induced by fluorescent whitener, and the luminescence can be irreversibly transformed into bright yellow (for 1 and 4) or red (for 3) simply by annealing treatment at 300 °C.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)