Solvation Effects on the Stability of Silver(I) Complexes with Pyridine-Containing Ligands Studied by Thermodynamics and DFT Methods

Piero, Silvia Del; Fedele, Rosalisa; Melchior*, Andrea; Portanova, Roberto; Tolazzi, Marilena; Zangrando, Ennio

doi:10.1021/ic800010g

Cited by 3 publications

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“…Solvation can strongly affect the relative thermodynamic stabilities of reaction products when passing from the gas phase to solution. [22][23][24][25] In our case, to take into account the effects of metal de-solvation and complex hydration on the preferential coordination mode with HL III , several [UO 2 (L III )-(H 2 O) n ·m(H 2 O)] + complexes (n = 0, 3, and 4; m = 0, 1, and 2; n + m = 0-5) have been considered. Geometry optimizations were first carried out in a vacuum and produced true minimum structures as no imaginary frequencies were found.…”

Section: Dft Calculationsmentioning

confidence: 99%

“…As far as the solvent effect on the energies is considered, a common practice is to use the gas-phase geometry and do the energy calculation in the presence of the polarizable continuum. 18,[26][27][28] However, in this work, re-optimization of the complex geometries was performed, starting from the energy-minimized gas-phase structures. The re-optimization produced slightly different minima (no imaginary frequencies) with only very small changes in the geometries of the complex and reagent structures (with the exception of bond lengths in some species, e.g., the species k and l discussed in a later section).…”

Section: Dft Calculationsmentioning

confidence: 99%

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Complexation of uranium(vi) with glutarimidoxioxime: thermodynamic and computational studies

et al. 2015

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The complex formation between a cyclic ligand glutarimidoxioxime (denoted as HL(III) in this paper) and UO2(2+) is studied by potentiometry and microcalorimetry. Glutarimidoxioxime (HL(III)), together with glutarimidedioxime (H2L(I)) and glutardiamidoxime (H2L(II)), belongs to a family of amidoxime derivatives with prospective applications as binding agents for the recovery of uranium from seawater. An optimized procedure of synthesis that leads to the preparation of glutarimidoxioxime in the absence of other amidoxime byproducts is described in this paper. Speciation models based on the thermodynamic results from this study indicate that, compared with H2L(I) and H2L(II), HL(III) forms a much weaker complex with UO2(2+), UO2(L(III))(+), and cannot effectively compete with the hydrolysis equilibria of UO2(2+) under neutral or alkaline conditions. DFT computations, taking into account the solvation by including discrete hydration water molecules and bulk solvent effects, were performed to evaluate the structures and energies of the possible isomers of UO2(L(III))(+). Differing from the tridentate or η(2)-coordination modes previously found in the U(vi) complexes with amidoxime-related ligands, a bidentate mode, involving the oxygen of the oxime group and the nitrogen of the imino group, is found to be the most probable mode in UO2(L(III))(+). The bidentate coordination mode seems to be stabilized by the formation of a hydrogen bond between the carbonyl group of HL(III) and a water molecule in the hydration sphere of UO2(2+).

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Section: Dft Calculationsmentioning

confidence: 99%

Section: Dft Calculationsmentioning

confidence: 99%

Complexation of uranium(vi) with glutarimidoxioxime: thermodynamic and computational studies

et al. 2015

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“…Inspired by previous reports on hexagonal self-assemblies from trans -capped Pt(II) precursors (Yang et al, 2007) and 120° bidentate pyridine-type ligands, which are known for their luminescent properties, and other luminescent Pt(II)-based metallacycles (Huang et al, 2017; Tang et al, 2018), we now report the self-assembly of hexagonal metallacycles from the same class of ligand donors and Ag(I) and Au(I) metal acceptors. There have been few reports on linear Ag(I) (Del Piero et al, 2008) and Au(I) (Fernández et al, 2007) complexes, and Ag(I) metallacycles (Shin et al, 2003; Chen and Mak, 2005; Fromm et al, 2005; Ren et al, 2006; Kim et al, 2009; Wan and Mak, 2011; Kole et al, 2012; Wei et al, 2012; Chevrier et al, 2013) with pyridine-type ligands, but these are the first Ag(I) and Au(I) hexagonal rings. We also synthesized Ag(I) and Au(I) monomeric complexes using analogous monodentate pyridine-type ligands.…”

Section: Introductionmentioning

confidence: 99%

Coordination-Driven Self-Assembly of Silver(I) and Gold(I) Rings: Synthesis, Characterization, and Photophysical Studies

et al. 2019

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In this work, we investigate the self-assembly between Ag(I) and Au(I) centers and pyridyl donors to form hexagonal metallacycles and related linear complexes. The precipitation of hexagonal metallacycles upon assembly in chloroform/methanol mixtures results in high solid-state photo-stability. Whereas, the Ag(I) species have fast kinetics and high formation constants in acetone, this solvent interferes in the formation of the analogous Au(I) complexes. The photophysical properties of this suite of metallacycles was investigated including steady-state absorption, emission, and time-resolved lifetime measurements. All ligands and hexagons exhibited ligand-centered singlet emissions with ground-state absorption and emission perturbed upon coordination. The ligand-based fluorescent photoluminescence was affected by the heavy-atom effect when halide or metals are present, attenuating quantum yields as evidenced by increases in the experimentally measured non-radiative rate constants. The formation of group 11 metallacycles is motivated by their potential applications in mixed-matrix materials wherein metal ions can interact with substrate to facilitate separations chemistry with reduced energy requirements, in particular the isolation of ethylene and light olefins. Existing processes involve cryogenic distillation, an energy intensive and inefficient method.

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“…This computational approach has been successfully employed to obtain reliable structural and thermochemical data for metal complex formation in the gas phase and aqueous solution. [24][25][26][27][28][29][30][31][32][33][34] The combined results from the thermodynamic studies and DFT calculations are used to propose a relationship between the stability in solution of the [M(PTA) 4 ][X] compounds (X = BF 4 − , PF 6 − , Fig. 1) and their cytotoxic activity.…”

Section: Introductionmentioning

confidence: 99%

Cu(i) and Ag(i) complex formation with the hydrophilic phosphine 1,3,5-triaza-7-phosphadamantane in different ionic media. How to estimate the effect of a complexing medium

et al. 2017

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Solvation Effects on the Stability of Silver(I) Complexes with Pyridine-Containing Ligands Studied by Thermodynamics and DFT Methods

Cited by 3 publications

References 0 publications

Complexation of uranium(vi) with glutarimidoxioxime: thermodynamic and computational studies

Complexation of uranium(vi) with glutarimidoxioxime: thermodynamic and computational studies

Coordination-Driven Self-Assembly of Silver(I) and Gold(I) Rings: Synthesis, Characterization, and Photophysical Studies

Cu(i) and Ag(i) complex formation with the hydrophilic phosphine 1,3,5-triaza-7-phosphadamantane in different ionic media. How to estimate the effect of a complexing medium

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