Interaction Between Group IIb Divalent Transition-Metal Cations and 3-Mercaptopropionic Acid: A Computational and Topological Perspective

Abstract

Density functional theory was applied to study the interaction of group IIb transition-metal cations (Zn(2+), Cd(2+), and Hg(2+)) with one and two fully or partially deprotonated 3-mercaptopropionic acid ligands. In this investigation, we determined the geometries of all possible complexes resulting from the coordination of the metal ions with the ligands at different binding sites selected on each ligand. The relative energies of the complexes, metal-ion affinities, free energies, and entropies were also determined. The natures of the bonds were critically analyzed by natural bond orbital (NBO) analysis and clarified further using the atoms-in-molecules (AIM) approach. The substantial influence of the solvent (water) polarization on the energetics, geometries, and bonding of the molecular complexes was also investigated by the conductor-like screening solvation model (COSMO). In an attempt to simulate the complexes in an aqueous environment, water molecules were added explicitly to complete the coordination sphere of the metal cations, and the corresponding metal-ion affinities were calculated to study the effect of microhydration.

Post-synthetic modification and chemical modulation of the ZIF-8 MOF using 3-mercaptopropionic acid (MPA): a multi-technique study on thermodynamic and kinetic aspects

“…This result can be ascribed to coordinative etching due to the known affinity between the carboxylate moieties of MPA and zinc ions. 52,53 Taking this into account, PSM was then carried out using lower MPA proportions; i.e., we employed a MeImH : MPA = 250 : 1 molar ratio, which was observed to yield the desired surface modification without compromising the ZIF-8 structure, as will be discussed in the next paragraphs. MPA was added then using the PSM strategy to a ZIF-8 colloidal suspension obtained after 1:30 h (90 min.)…”

“…Within suitable concentration limits, MPA affects the particle formation kinetics, size polydispersity, and morphology of ZIF-8, while preserving the SOD topology, which is the most stable from the possible polymorphs arising when Zn 2+ ions and 2-methylimidazole react. 51 The reason behind the election of MPA which features -SH and -COOH moieties is to take advantage of the known affinity between Zn 2+ and carboxylic acid, 52,53 for the design of sizecontrolled thiolate-terminated porous colloidal nanounits. 54 These nanounits would then display affinity towards metallic surfaces (e.g., Au, Pt), thus opening a diverse palette for the assembly of monolayers or decoration of diverse metallic nanostructures, adding the interesting feature of porosity.…”

Complexation of Bi(iii) with 3-mercaptopropionic acid in aqueous solutions: a combined experimental and theoretical study

“…3-mercaptopropionic acid commonly forms complex species of cyclic S,O-chelate structures. 8,18 However, it also forms polymeric S-bridged structures with Pd(II) and Pt(II) 16,17 and Obridged polymers with Gd(III), Eu(III) and Tb(III). 15 No bidentate coordination of carboxylic functional group in [Bi(MPA) 2 ] À is observed (DFT) so this complex is likely to have polymeric structure.…”

“…Such ligand coordination is consistent with previous reports. 8,[15][16][17][18] The optimized geometry corresponds to the C 2 point symmetry group. The results of EXAFS spectroscopy investigation and of DFT simulation are given in Table 7.…”

“…7 There are multiple reports focused on complexation of H 2 MPA with Zn(II), Ni(II), In(III), Cd(II), Hg(II), Co(III) Lanthanides(III), Pd(II) and Pt(II). [8][9][10][11][12][13][14][15][16][17][18][19][20][21] The reason for the choice of bismuth(III) ion is essentially due to the fact that bismuth compounds have attracted attention recently because of their multiple applications in diverse areas including medicine materials and material sciences. The medicinal application of bismuth compounds is focused in two elds: antimicrobial and anticancer.…”