Polar layered coordination polymers incorporating triazacyclononane-triphosphonate metalloligands

Abstract

Reactions of metalloligands M^III(notpH₃) (M = Fe, Co and notpH₆ = 1,4,7-triazacyclononane-1,4,7-triyl-tris(methylenephosphonic acid)) with Zn(OAc)₂ under hydrothermal conditions resulted in new metal phosphonates Zn₂Fe(notp)Cl(H₂O) (1) and ZnCo(notpH)(H₂O)·2H₂O (2). They crystallize in polar space groups P6₃ (for 1) and Pca2₁ (for 2), respectively, and exhibit layer structures in which the inorganic layers are separated by the organic groups of the notp ligands. However, the layer topologies of the two compounds are quite different. In 1, the layer contains 6-membered rings composed of one {FeN₃O₃} octahedron, one {Zn1O₃Cl}, one {Zn2O₄} and three {PO₃C} tetrahedra via corner-sharing connections, while in 2, the layer contains 10-membered rings composed of two {CoO₃N₃} octahedra, three {ZnO₄} and five {PO₃C} tetrahedra via vertex-sharing connections. Dielectric measurements on single crystals of 2 confirmed the presence of high dielectric anisotropy. Proton conductivity measurements revealed that the proton conduction is more favourable in 2 due to the presence of a continuous hydrogen bond network in this compound.