From Cubane to Supercubane: The Design, Synthesis, and Structure of a Three-Dimensional Open Framework Based on a Ln4O4 Cluster

Abstract

An extended network, {[Dy4(OH)4(asp)3(H2O)8](ClO4)2⋅10 H2O}n, having three‐dimensional channels with a spacing of 11.78 Å (see picture) has been prepared by mixing Dy(ClO4)3 and L‐aspartic acid in aqueous solution, and subsequently adjusting the pH values to about 6.5 using aqueous NaOH solution. This open‐framework compound is representative for the assembly of discrete lanthanide cubanes into supercubanes.

Lanthanides: Amino Acid Compounds

“…[38][39][40][41] Minor discrepancies exist among these complexes, however. Although in most of these complexes, the amino acid ligands are zwitterionic with the amino group remaining protonated, there are examples such as [Gd 4 (μ 3 -OH) 4 10 ] 8+ .…”

Synthesis and Spectroscopic Characterization of <i>l</i>-Aspartic Acid Complexes with Metals of the Lanthanides Family

“…3 An aqueous solution of lanthanum perchlorate was prepared by digesting (0.65 gm) La 2 O 3 in concentrated perchloric acid (2 ml, 70 %), a suitable concentration of La(ClO 4 ) 3 (1.9 g, 4 mmol) was achieved by diluting the concentrated solution with 10 ml distilled water, laspartic acid (0.266 g, 2 mmol) was added as solid to the above aqueous solution of La(ClO 4 ) 3 , one drop of an aqueous solution of HCl (1.0 M) was then added. The mixture was stirred at about 80 °C on a heating plate while an aqueous solution of NaOH (0.5 M) was added dropwise to cause an incipient but permanent precipitate, pH = 5.…”

“…They differ in the alkyl group (-R) attached to the C in α position. Among the natural amino acids there are two dicarboxylates, namely l-aspartic acid (asp) and l-glutamic acid (glu), these not only retain the nature of the amino acids but also possess bridging capability [3]. Figure 2) whose constituent lanthanides ions and triply bridging hydroxo groups occupy the alternate vertexes of a distorted cube [11] .…”

Luminescence and Magnetic Properties of Two Three-Dimensional Terbium and Dysprosium MOFs Based on Azobenzene-4,4′-Dicarboxylic Linker

“…The chemistry of Lanthanide-based MOFs has been significantly less explored than that of transition metal-based MOFs, probably due to the fact that lanthanide elements are usually regarded as unsuitable metal centers, as coordination numbers are too high and coordination geometries are hard to control. Over the past few years, however, the design and study of Lanthanide-based MOFs has evolved enormously [4][5][6][7][8][9] because of their interesting structures and potential applications in areas such as luminescent materials [10], enormously [4][5][6][7][8][9] because of their interesting structures and potential applications in areas such as luminescent materials [10], selective gas adsorption [11], magnetism [12], sensors, and biological properties [13]. Given that, classically, the first scientific efforts were focused on the use of MOF as possible porous materials for gas storage and separation, the study of their luminescent and magnetic properties have been forgotten.…”