Syntheses, Crystal Structures, and Characterizations of a Series of New Layered Lanthanide Carboxylate‐Phosphonates

Hydrothermal reactions of different lanthanide(III) salts with (H2O3PCH2)2NCH2COOH (H5L1) led to two new layeredlanthanide(III) carboxylate‐diphosphonates, namely La(H2L1)(H2O)2·H2O (1) and La(H2L1)(H2O) (2). The structure of compound 1 features a layered architecture in which the nine‐coordinate La3+ ions are bridged by phosphonate groups of the ligands. The carboxylate group of the phosphonate ligand remains protonated and is involved in the interlayer hydrogen bonding. Compound 2 features a double layer structure in which the La3+ ion is eight‐coordinated and the carboxylate group of the ligand is chelated to a La3+ ion in a bidentate fashion. Hydrothermal reactions of lanthanide(III) salts with 4‐HOOC–C6H4–CH2N(CH2PO3H2)2 (H5L2) afforded three new compounds, namely, La(H4L2)(H3L2)(H2O)·2H2O (3), Er(H3L2)(H4L2) (4), and Er(HL3)(H2L3)(H2O) (5) [H2L3 = H2O3PCH2N(CHO)(CH2–C6H4–COOH)]. H2L3 was formed by the in situ oxidation of one P–C bond of the H5L2 ligand. Compound 3 features a (002) lanthanum(III) phosphonate layer in which the seven‐coordinate La3+ ions are bridged by diphosphonate moieties of the ligands. The carboxylate group remains protonated and is involved in the interlayer hydrogen bonding. The structure of compound 4 contains a 1D chain along the a axis in which each pair of ErO6 octahedra is bridged by a pair of phosphonate groups. These 1D chains are further interconnected by hydrogen bonds between noncoordinated phosphonate oxygen atoms into a (002) layer with the phenyl carboxylate groups hanging on the interlayer space. The structure of compound 5 is also layered. The interconnection of Er3+ ions by bidentate and tetradentate bridging phosphonate groups resulted in a (002) inorganic layer with the organic groups orientated to the interlayer space. Luminescence properties of compounds 4 and 5 have also been studied.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)