Synthesis and Structural Characterization of Nonanuclear Lanthanide Complexes

Abstract

A series of nonanuclear lanthanide oxo-hydroxo complexes of the general formula [Ln(9)(mu(4)-O)(2)(mu(3)-OH)(8)(mu-BA)(8)(BA)(8)](-)[HN(CH(2)CH(3))(3)](+).(CH(3)OH)(2)(CHCl(3)) (BA = benzoylacetone; Ln = Sm, 1; Eu, 2; Gd, 3; Dy, 4; Er, 5) were prepared by the reaction of hydrous lanthanide trichlorides with benzoylacetone in the presence of triethylamine in methanol and recrystallized from chloroform/methanol (1:10) at room temperature. These five compounds are isomorphous. Crystal data for 1: cubic, Pn3n; T = 180 K; a = 33.8652(4) A; V = 38838.4(8) A(3); Z = 6; D(calcd) = 1.125 g cm(-)(3); R1 = 3.37%. Crystal data for 2: cubic, Pn3n; T = 180 K; a = 33.8252(8) A; V = 38700.9(16) A(3); Z = 6; D(calcd) = 1.133 g cm(-)(3); R1 = 4.97%. Crystal data for 3: cubic, Pn3n; T = 180 K; a = 33.7061(6) A; V = 38293.5(12) A(3); Z = 6; D(calcd) = 1.157 g cm(-)(3); R1 = 5.13%. Crystal data for 4: cubic, Pn3n; T = 180 K; a = 33.5900(7) A; V = 37899.2(14) A(3); Z = 6; D(calcd) = 1.182 g cm(-)(3); R1 = 4.03%. Crystal data for 5: cubic, Pn3n; T = 180 K; a = 33.5054(8) A; V = 37613.6(16) A(3); Z = 6; D(calcd) = 1.202 g cm(-)(3); R1 = 4.86%. The core of the anionic cluster comprises two vertex-sharing square-pyramidal [Ln(5)(mu(4)-O)(mu(3)-OH)(4)](9+) units. The compounds were characterized by elemental analysis, IR, fast atom bombardment mass spectra, thermogravimetry, and differential scanning calorimetry. The thermal analysis indicated that the nonanuclear species were stable up to 150 degrees C. Luminescence spectra of 2 and magnetic properties of 1-5 were also studied.

Rare‐Earth Metal Oxo/Hydroxo Clusters – Synthesis, Structures, and Applications

“…The resulting nonanuclear cluster compounds are stabilized by oxo-or hydroxo groups in the inner coordination sphere and by various ligands in the outer coordination sphere (Figure 2). Examples with alkoxides, [39] -diketonates, [7,52,57,58] and pyridine derivatives [59] are known in the literature. Hydrogen atoms are omitted for clarity.…”

“…Hydrogen atoms are omitted for clarity. [57] As stated above, a tetradecanuclear cluster core exhibiting four square pyramid units is also known in the literature, [37][38][39] with the square pyramidal building blocks being attached to each other by sharing their basal faces or their vertices (Scheme 2).…”

Tetranuclear Lanthanide Aqua Hydroxo Complexes with Macrocyclic Ligand Cucurbit[6]uril

“…In general, the ESI-MS allow identification of the intact sandwich complexes [Gd 4 (OH) 8 4+ . These species are typically observed to different extents as proton, HCl and/or H 2 O adducts and in consequence appear as 3+, 4+, and 5+ charged cations.…”

Chemical‐Bonding Assembly, Physical Characterization, and Photophysical Properties of Lanthanide Hybrids from a Functional Thiazole Bridge

“…It is deduced that the adsorbed water and residual solvent evaporated, without any decomposition of the chemical bonds. [32] As the temperature exceeds 200°C, the complex begins to decompose. The whole mass loss may be explained by the thermal instability of the organic parts.…”