Orthogonal effect of exchange and correlation parameters in density functional theory to compute geometric and spectroscopic quantities.

The influence of the composition of the functional used for density functional theory computations on one structural parameter (a dihedral angle) and a spectroscopic parameter (absorption wavelength) is assessed in this study on the basis of two molecules (flavonols). In this kind of molecules, these two parameters should be correlated according to the nature of the electronic transition involved. However, it is shown herein that by varying the proportion of true exchange and correlation while building a functional, it is possible to obtain independently a large range of values for these parameters without any relation with the underlying real values.

Stability of Iodine Species Trapped in Titanium-Based MOFs: MIL-125 and MIL-125_NH.

Two titanium-based MOFs MIL-125 and MIL-125_NH are synthesized and characterized using high-temperature powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), N sorption, Fourier transformed infrared spectroscopy (FTIR), Raman spectroscopy, ultraviolet-visible spectroscopy (UV-Vis), and electron paramagnetic resonance (EPR). Stable up to 300 °C, both compounds exhibited similar specific surface areas (SSA) values (1207 and 1099 m g for MIL-125 and MIL-125_NH, respectively). EPR signals of Ti are observed in both, whith MIL-125_NH also showing ─NH signatures.

New insights for titanium(iv) speciation in acidic media based on UV-visible and P NMR spectroscopies and molecular modeling.

Titanium chemistry in aqueous acidic media has been extensively investigated over the last decades. Hydrolyzed species such as Ti(OH), TiO, Ti(OH) or Ti(OH) have been identified and their equilibria have been studied in nitric and perchloric acid. A predominance of the divalent cations was found for low pH (, pH <2).

pH dependency of the structural and photophysical properties of the atypical 2',3-dihydroxyflavone.

2',3-Dihydroxyflavone (2'3HF) is a natural flavonol that has barely ever been studied, however the scarce studies of its physico-chemical properties have highlighted its atypical behaviour. We present a structural and spectral study of 2'3HF, performed using UV-visible absorption and fluorescence spectroscopies, coupled with DFT and TD-DFT calculations. Although its structure is close to that of 3-hydroxyflavone, 2'3HF shows a much lower p value.

Spectroscopic and theoretical study of the pH effect on the optical properties of the calcium-morin system.

Morin (2-(2,4-dihydroxyphenyl)-3,5,7-trihydroxychromen-4-one) is an abundant flavonoid with various pharmacological and biological activities. Considering the ubiquitous presence of calcium cations in biological systems, it seems relevant to study the interaction of this ion with morin and the influence of pH on this system. In a first step, among the four hypothetical chelation sites, the preferential fixing site, its protonation state and the Ca environment have been determined by combining electronic spectroscopies and density functional theory (DFT) and time-dependent DFT calculations.

Electronic Spectroscopies Combined with Quantum Chemistry Calculations: Study of the Interactions of 3-Hydroxyflavone with Copper Ions.

The current study aims at obtaining a better understanding of the mechanisms involved in the complexation of copper ions by 3-hydroxyflavone (3HF), which is one of the most studied compounds of the flavonoid family. To achieve this goal, quantum chemistry calculations combined with electronic spectroscopies, including absorption, fluorescence emission, and excitation, have been used. The formation of successive complexes of stoichiometry (metal/ligand) 1:2, 1:1, and 3:2 has been highlighted.

Visible light-triggered fluorescence and pH modulation using metastable-state photoacids and BODIPY.

Small changes in the pH gradient play a critical role in numerous biological and chemical pathways. Systems capable of monitoring and regulating these changes with high sensitivity and minimum photo-fatigue are in demand. Herein, we propose a visible light-triggered molecular system that allows for reversible regulation of acidity and fluorescence.

Chalcogen substitution: Effect of oxygen-by-sulfur exchange on structural and spectroscopic properties of flavonols.

Quantum chemical calculations using density functional theory have revealed that the substitution of the ketone group by a thioketone one doesn't significantly change the structure of 3-hydroxyflavone. Notably, the strong intramolecular hydrogen bond involving the hydroxyl function is preserved if the O atom is substituted by an S atom, but also by Se or Te atoms. However, fundamental modifications are observed in both absorption and emission electronic spectra upon substitution, particularly the non-fluorescent behavior of the flavothione.

A quantum chemistry evaluation of the stereochemical activity of the lone pair in Pb complexes with sequestering ligands.

The stereochemical activity of the lone pair on Pb complexes is assessed using several theoretical methods, including structural analyses, computations of Fukui functions, natural bond orbitals, electron localization function, investigation of the electron density and of its laplacian. The attention is focused on four octadentate N-carbamoylmethyl-substituted tetraazamacrocycles of various ring sizes ranging from 8 to 14 atoms associated with the Pb cation. The theoretical study illustrates the geometrical constraints imposed by the ring structure which limits the spatial development of the lone pair but without fully preventing it.

Direct Carboxylation of Aryl Tosylates by CO2 Catalyzed by In situ-Generated Ni(0).

A novel Ni(0) -catalyzed carboxylation of aryl tosylates with carbon dioxide has been achieved under moderate temperatures and atmospheric pressure. In this procedure, the active Ni(0) species is generated in situ by simply mixing the Ni(0) precatalyst [NiBr2 (bipy)] with an excess of manganese metal. This approach requires neither a glove-box nor the tedious preparation of sophisticated intermediate organometallic derivatives.

Conformational and structural studies of N-methylacetohydroxamic acid and of its mono- and bis-chelated uranium(VI) complexes.

The thermodynamics and kinetics of the cis/trans isomerism of N-methylacetohydroxamic acid (NMAH) and its conjugated base (NMA(-)) have been reinvestigated in aqueous media by (1)H NMR spectroscopy. Hindered rotation around the central C-N bond due to electronic delocalization becomes slow enough on the NMR time scale to observe both rotamers in equilibrium in D2O at room temperature. By properly assigning the methyl group resonances, evidence for the prevalence of the E over the Z form is unambiguously provided [K300=[E]/[Z]=2.

Enantioselective organocatalytic partial transfer hydrogenation of lactone-fused quinolines.

The first enantioselective synthesis of 4-aza-podophyllotoxin derivatives by partial transfer hydrogenation of lactone-fused quinolines was achieved using a chiral Brønsted acid catalyst. This reaction was extended to a large scope of substrates with good yields and enantioselectivities.

The complexation of AlIII, PbII, and CuII metal ions by esculetin: a spectroscopic and theoretical approach.

UV-visible absorption spectroscopy combined with quantum chemical calculations and, notably, Time-Dependent Density Functional Theory were used to probe the structure of metal complexes with esculetin in dilute aqueous solution, at pH = 5. For the 1:1 complex formation, the studied metal ions can be classified according to their complexing power: aluminum(III) > copper(II) > lead(II). For the three complexes, a chelate is formed with the fully deprotonated catechol moiety and an absorption band is observed at the same wavelength.

Enhancement of the water solubility of flavone glycosides by disruption of molecular planarity of the aglycone moiety.

Enhancement of the water solubility by disruption of molecular planarity has recently been reviewed as a feasible approach in small-molecule drug discovery programs. We applied this strategy to some natural flavone glycosides, especially diosmin, a highly insoluble citroflavonoid prescribed as an oral phlebotropic drug. Disruption of planarity at the aglycone moiety by 3-bromination or chlorination afforded 3-bromo- and 3-chlorodiosmin, displaying a dramatic solubility increase compared with the parent compound.

Cobalt-catalyzed vinylation of aromatic halides using β-halostyrene: experimental and DFT studies.

A new protocol for the direct cobalt-catalyzed vinylation of aryl halides using β-halostyrene has been developed in order to form functionalized stilbenes. A variety of aromatic halides featuring different reactive group were employed. This method proceeded smoothly with a total retention of the double bond configuration in the presence of triphenylphosphine as ligand.

Theoretical study of absorption and emission properties of green and yellow emitting iridium(III) complexes.

Iridium(III) complexes are among the most used phosphorescent materials for the development of organic light emitting diodes (OLEDs). In this work, the photophysical properties of a family of complexes based on phenyldiazine ligands were studied. Their ground state geometric and electronic structures as well as their absorption and emission spectra were investigated by the means of density functional theory (DFT) and time-dependent DFT (TD-DFT).

Cobalt-catalyzed formation of symmetrical biaryls and its mechanism.

Effective devotion: An efficient cobalt-catalyzed method devoted to the formation of symmetrical biaryls is described avoiding the preparation of organometallic reagents. Various aromatic halides functionalized by a variety of reactive group reagents are employed. Preliminary DFT calculations have shown that the involvement of a Co(I)/Co(III) couple is realistic at least in the case of 1,3-diazadienes as ligands (FG = functional group).

Cobalt-catalyzed cross-coupling reactions.

In the last few years, we and other groups have demonstrated that economical cobalt salts can advantageously replace expensive and toxic catalysts for cross coupling reactions. These cobalt-catalyzed reactions have considerably extended the range of functionalized compounds. A variety of sensitive functional groups can be tolerated in these coupling reactions and various organic compounds RX could be involved (R = alkyl, alkynyl, aryl, allyl and X = halides: F, Cl, Br, I and even triflates).