Thermodynamic and Kinetic Control on the Formation of Two Novel Metal-Organic Frameworks Based on the Er(III) Ion and the Asymmetric Dimethylsuccinate Ligand

• Published in: Inorganic chemistry Vol. 49; no. 11; pp. 5063 - 5071
• Main Authors: Bernini, María C, de la Peña-O’Shea, Victor A, Iglesias, Marta, Snejko, Natalia, Gutierrez-Puebla, Enrique, Brusau, Elena V, Narda, Griselda E, Illas, Francesc, Monge, M. Ángeles
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 07-06-2010
• Subjects: Computer Simulation; Crystallography, X-Ray; Erbium - chemistry; Ions - chemistry; Kinetics; Ligands; Models, Molecular; Organometallic Compounds - chemical synthesis; Organometallic Compounds - chemistry; Succinates - chemistry; Thermodynamics
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic100181d

Two new layered polymeric frameworks have been synthesized under different hydrothermal conditions and characterized by single-crystal X-ray diffraction, thermal analysis, and variable temperature-Fourier Transform Infrared Spectroscopy (VT-FTIR). The compound I, with formula [Er2(dms)3(H2O)4], has a triclinic cell with parameters a = 5.8506 Å, b = 9.8019 Å, c = 11.9747 Å, α = 70.145°, β = 80.234°, and γ = 89.715°, and the compound II, [Er2(dms)3(H2O)], is monoclinic and its cell parameters are a = 11.1794 Å, b = 18.2208 Å, c = 12.7944 Å, β = 112.4270°, where dms = 2,2-dimethylsuccinate ligand. A theoretical study including energy calculations of the dms conformers was carried out at the Density Functional Theory (DFT-B3LYP) level of theory, using the 6-311G* basis set. Further calculations of the apparent formation energies of I and II crystalline structures were performed by means of the periodic density functional theory, using DF plane-waves. The analysis of the structural features, theoretical relative stabilities, and the influence of synthesis conditions are presented here. The heterogeneous catalytic activity of the new compounds is tested and reported.