Rational Design of 0D, 1D, and 3D Open Frameworks Based on Tetranuclear Lanthanide(III) Sulfonate−Phosphonate Clusters

Abstract

Hydrothermal reactions of lanthanide(III) salts with m-sulfophenylphosphonic acid (H3L1) and 1,10-phenanthroline (phen) or N,N'-piperazinebis(methylenephosphonic acid) (H4L2) afforded six novel lanthanide(III) sulfonate-phosphonates based on tetranuclear clusters, namely, [La(2)(L1)2(phen)4(H2O)].4.5H2O (1), [Ln2(L1)2(phen)2(H2O)5].3H2O (Ln = Nd, 2; Eu, 3; Er, 4), and [Ln2(HL1)(H2L2)2(H2O)4].8H2O (Ln = La, 5; Nd, 6). Compounds 2-4 contain discrete tetranuclear lanthanide(III) cluster units in which four lanthanide(III) ions are bridged by two tridentate and two tetradentate phosphonate groups. In compound 1, the tetranuclear clusters are further interconnected into a 1D chain through the coordination of the sulfonate groups. The structures of compounds 5 and 6 can be viewed as a 3D architecture based on a different types of tetranuclear cluster units that are interconnected by bridging H2L2 anions. In the tetranuclear clusters of compounds 5 and 6, the four lanthanide(III) centers are interconnected by only two HL1 ligands. Compound 2 is a luminescent material in the near-IR region, whereas compound 3 displays a strong luminescent emission band in the red-light region. Magnetic property measurements of compounds 2-4 and 6 indicate that there are strong antiferromagetic interactions between magnetic centers within the cluster units.

Systematic Hydrothermal Investigation of Metal Phosphonatobenzenesulfonates by High‐Throughput Methods

“…[29,30] Rigid phosphonoarylsulfonic acids, i.e. 3-phosphonobenzenesulfonic were employed by Mao et al, [31][32][33][34][35] 5-phosphono-1,3-disulfonic acid and 4-fluoro-3-sulfobenzylphosphonic acid by Montoneri et al, [36,37] mostly in combination with amine linkers. The synthesis of most metal phosphonates is accomplished under hydrothermal conditions.…”

Crystal structure of poly[bis(μ2-aqua-triaqua)[μ2-piperazine-1,4-diylbis-(methylene)diphosphonato-κ2O:O′]disodium(I)] dihydrate, C3H17NNaO8P

“…In particular, piperazine-1,4-diylbis(methylene)diphosphonic acid (H 4 L) formsw ide structures with arange of metal cations as it can bind through two to eight of O/N atomsper ligand. These complexes exhibit luminescent [1][2][3], magnetic [1,[4][5][6] and gas adsorption properties [7][8][9][10][11].H owever, mosto ft he earlier investigations based on the ligand have been concentrated on the divalent transition [12][13][14] and trivalent lanthanide metals [7,8,12,13,15].The main group metal complexes have been rarely reported [16-18,3 ,1 0].T he asymmetric unit contains one Na + ion, one half H 2 L 2-,four coordinatedwater an<d onelattice watermolecule. TheNa + ion is sixcoordinated with adistorted octahedral geometry.…”

Synthesis, Crystal Structures, and Magnetic Properties of Lanthanide (III) Amino-Phosphonate Complexes

“…(1-amino-1-cyclohexyl) phosphonic acid synthesized according to the reported method [59]. [Ln 2 (O 2 C t Bu) 6 (HO 2 C t Bu) 6 ] (Ln = Gd(III); Tb(III)) were synthesized following the reported procedure [60,61]. Analytical data were obtained by the microanalytical service of the University of Manchester.…”

“…In recent years, research involving metal phosphonates has been deeply explored because of the great variety of building blocks available for the preparation of functional materials useful in the field of structural chemistry and magnetic properties [1][2][3][4][5][6][7]. Phosphonic acid and its derivatives are flexible coordination ligands towards a wide range of metal ions, with various ionic radii, including Ln(III) ions, resulting in some materials with promising magnetic properties [8][9][10][11].…”