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

Abstract

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 [Er(2)(dms)(3)(H(2)O)(4)], has a triclinic cell with parameters a = 5.8506 A, b = 9.8019 A, c = 11.9747 A, alpha = 70.145 degrees , beta = 80.234 degrees , and gamma = 89.715 degrees , and the compound II, [Er(2)(dms)(3)(H(2)O)], is monoclinic and its cell parameters are a = 11.1794 A, b = 18.2208 A, c = 12.7944 A, beta = 112.4270 degrees , 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.

Reviewing Rare Earth Succinate Frameworks from the Reticular Chemistry Point of View: Structures, Nets, Catalytic and Photoluminescence Applications

“…The inorganic chains are linked by two crystallographic independent succinate anions resulting in a 2D organic‐inorganic framework. H‐bonds involving hydration and coordination water molecules along with oxygen atoms from carboxylate groups ensure the packing.2D‐3 structural type was reported for erbium, yttrium and lutetium frameworks based on the 2,2‐dms ligand. Different space groups (S.G.) were reported, P 1 being for the erbium compound, and P ī for the yttrium and lutetium ones.…”

“…Different space groups (S.G.) were reported, P 1 being for the erbium compound, and P ī for the yttrium and lutetium ones. In the case of the Er 3+ framework, to rule out the centrosymmetric space group and the existence of a non‐resolvable positional disorder, the structure was solved in the P 1 S.G., where the occupation factors of the methyl groups of the trans dms anion were equal to 1. If such disorder would exist, the occupation factors of these methyl groups should have been 1/2 also in the P 1 S.G.…”

“…Unlike in 2D‐1 and 2D‐2 structural types where the layers are linked together by a complex H‐bonding subnet developed by hydration water molecules located in the interlayer space, the layers in 2D‐3 stack three‐dimensionally through London dispersion forces involving the methyl groups of the linker. Additionally, an H‐bond interaction between two coordinated water molecules belonging to adjacent layers was also identified2D‐4 ([Ln 2 (dms) 3 (H 2 O)] and [Ln 2 (psa) 3 (H 2 O)]) was reported for frameworks based on several Ln 3+ ions and 2,2‐dms, or 2‐psa, ligands (see Figure ). Among the structures based on both ligands there are subtle differences mainly associated with the coordination modes; however, such differences are not significant enough to change the structural type resulting in a set of isomorphic structures that are represented by a fes underlying net.…”

Synthesis, Structures, and Luminescent Properties of Two Four‐connected Polymers Based on 2, 2‐Dimethylsuccinic Acid

“…found that this ligand tend to construct polynuclear coordination polymers, meanwhile, the polymers based on this ligand have been less explored, [17][18][19][20][21] and (3) …”

Two Novel Self-Assembly CdII Coordination Polymers: Single-or Double 1D Chain Controlled by Ratio Change in Solvent and Their Photoluminescence Property

“…The complexes can be obtained by the reactions of the same ligand with the same center metal via controlling synthetic conditions such as counterions, pH value, reaction solvent, and the ratio of metal/ligand [22][23][24][25][26]. In this paper, we obtained two 3D supramolecular coordination polymers from 1D structure via controlling Electronic supplementary material The online version of this article (doi:10.1007/s10904-015-0237-y) contains supplementary material, which is available to authorized users.…”