Are DFT Methods Able to Predict Reduction Potentials of Ruthenium Nitrosyl Complexes Accurately?

The nitric oxide (NO) molecule is directly related to important physiological and physiopathological processes. Ruthenium tetraammine nitrosyl complexes can release NO from the [RuIINO+]3+/[RuIINO0]2+ reduction potential. Experimentally, well established is the practice of determining the redox potential with relation to a reference redox pair. However, there is no agreement on the best methodology that allows the minimization of uncertainties, both experimental and theoretical results. Here, the reduction potential relative to a reference redox pair is obtained from calculated absolute potentials for the target complex: trans-[Ru(NO)(L)(NH3)4]3+/2+ and reference pair: [Ru(bpy)3]3+/2+. The correlation between the calculated and experimental reduction potentials strongly depend on the DFT functional chosen. The best results were obtained with the GGA functional BP86, which showed deviations lower than 200 mV. The assignment of explicit solvent, in addition to continuum solvent influence, also appears as a relevant factor.

Synthesis, characterization and biological evaluation of new manganese metal carbonyl compounds that contain sulfur and selenium ligands as a promising new class of CORMs.

Three new manganese carbonyl compounds with heavy atom donors were synthesized and their potential use as photoCORMS was evaluated. Interestingly, all compounds had an elusive binding mode, in which the ligands adopted a κ2-X coordination (where X = S or Se), confirmed both by X-ray crystallography and IR spectroscopy. The stability of the title compounds in the dark was determined by monitoring the changes in the UV spectra of the compounds in both dichloromethane and acetonitrile. These studies show that in coordinating solvents there is an exchange of the bromide bonded to the metal centre by a solvent molecule, which is evidenced by the changes in the UV and IR spectra and by DFT analysis. EDA and natural bond order analyses were conducted to evaluate the influence of the heavy atom donors in the first coordination sphere of the compounds. Photoexcitation at 380 nm demonstrated that all compounds showed release of all three COs, as seen in the photoproducts detected by IR spectroscopy. Furthermore, CO release was observed when the photoCORMs were incubated with living cells, and we observed a CO-dependent inhibition of cell viability.

Synthesis and Solvatochromism of Substituted 4-(Nitrostyryl)phenolate Dyes.

4-(Nitrostyryl)phenols 2a-9a were synthesized, and by deprotonation in solution, the solvatochromic phenolates 2b-9b were formed. Their absorption bands in the vis region of the spectra are due to π-π* electronic transitions, of an intramolecular charge-transfer nature, from the electron-donor phenolate toward the electron-acceptor nitroarene moiety. The frontier molecular orbitals and natural bond orbitals were analyzed for the protonated and deprotonated forms. The calculated geometries are in agreement with X-ray structures observed for 4a, 6a, and 8a. The HOMO-LUMO energy gaps suggest that, after their deprotonation, an increase in the electron delocalization is observed. In the protonated compounds, the HOMO is primarily localized over the phenol ring and the C═C bridge. After deprotonation, it extends toward the entire molecule, including the NO2 groups. The solvatochromism of each dye was studied in 28 organic solvents, and it was found that all compounds exhibit a reversal in solvatochromism, which is interpreted in terms of the ability of the media to stabilize their electronic ground and excited states to different extents. The Catalán multiparameter equation is used in the interpretation of the solvatochromic data, revealing that the most important contribution to the solute/solvent interaction is the hydrogen-bond donor acidity of the solvent.

Ureasil-poly(ethylene oxide) hybrid matrix for selective adsorption and separation of dyes from water.

Herein, we present a cross-linked ureasil-polyether-siloxane hybrid (labeled PEO500) that can function as a stimuli-sensitive material; it swells or shrinks in response to changes in the environmental conditions and it can also, effectively and selectively, remove dyes from water solution. We also developed a methodology to separate a mixture of cationic and anionic dyes present in water. Addition of PEO500 to an aqueous solution of the anionic orange II (OII) or the ponceau S (PS) dye rendered the solution colorless, but an aqueous solution of cationic methylene blue (MB) remained unchanged after 2 h of contact with the insoluble matrix. In situ small-angle X-ray scattering (SAXS) showed that the distance of siloxane nanodomains are strongly affected by the swelling or shriking. By in situ UV-vis adsorption experiments, we found that the kinetics of OII and PS removal followed a pseudo-first-order rate equation. We accomplished B3LYP calculations, to establish which sites on the matrix interacted with the dyes and to investigate the nature of the matrix-dye chemical bonds. On the basis of the experimental and theoretical investigations, we proposed some mechanisms to explain how PEO500 adsorbs anionic dyes efficiently. This "smart" matrix is potentially applicable as an efficient, fast, selective, and convenient device in water treatment and stimuli-sensitive response materials.