Search results for "solvent effect"

2020

The course of organic chemical reactions is efficiently modelled through the concepts of “electrophiles” and “nucleophiles” (meaning electron-seeking and nucleus-seeking reactive species). On the one hand, an advanced approach of the correlation of the nucleophilicity parameters N and electrophilicity E has been delivered from the linear free energy relationship log k (20 °C) = s(N + E). On the other hand, the general influence of the solvent mixtures, which are very often employed in preparative synthetic chemistry, has been poorly explored theoretically and experimentally, to date. Herein, we combined experimental and theoretical studies of the solvent influence on pyrrolidine nucleophili…

Solvent effects on the dimensionality of oxamato-bridged manganese(II) compounds

2018

Two new oxamate-containing manganese(II) complexes, [{Mn(H2edpba)(H2O)2}2]n (1) and [Mn(H2edpba)(dmso)2]∙dmso∙CH3COCH3∙H2O (2) (H4edpba = N,N′-ethylenediphenylenebis(oxamic acid) and dmso = dimethylsulfoxide), have been synthesized and the structures of 1 and 2 were characterized by single crystal X-ray diffraction. The structure of 1 consists of neutral honeycomb networks in which each manganese(II) is six-coordinate by one H2edpba2− ligand and two carboxylate–oxygens from two other H2edpba2− ligands building the equatorial plane. Each manganese is connected to its nearest neighbor through two carboxylate(monoprotonated oxamate) bridges in an anti-syn conformation. A dmso solution of singl…

Solvent dependence of the νs(OD) bandshape in 2,6-dichlorophenol

1994

Abstract The infrared bandshape of νs(OD) of 2,6-dichlorophenol is measured in a series of solvents of increasing polarity, and is quantitatively analysed. The bandshape is described in terms of band indices, moments, correlation functions and correlation times. A distinct solvent dependence of bandshape and relaxation parameters has been found. The changes of the νs(OD) bandshape with increasing solvent polarity are compared in detail with those obtained earlier for analogous solvents for νs(OH) of 2,6-dichlorophenol. The overall behaviour of the spectral and relaxation parameters is similar, but the changes are less distinct for the weaker OD ⋯ Cl bond.

Acidochromism of the luminescence of bis(4-pyridylethenyl)arenes

2004

Abstract A series of C 2 -symmetrical bis[( E )-2-(4-pyridyl)ethenyl]arenes has been synthesised via two-fold PO-activated olefinations. 1,4-Benzene, 1,4-naphthalene, 9,10-anthracene and 2,2′-diphenyl were used as central units. These fluorescent compounds were freely soluble in common solvents. The absorption and the emission were sensitive towards solvent polarity and acid, in solution as well as in the solid state. Depending on the concentration of acid, protonation of the ground state and/or the excited state caused reductions of the fluorescence efficiencies, accompanied by bathochromic shifts of the absorption and the emission spectra of some chromophores. The title compounds, except …

Highly stereoselective tandem aza-Michael addition-enolate protonation to form partially modified retropeptide mimetics incorporating a trifluoroalan…

2003

Aminoacid zwitterions in solution : Geometric, energetic, and vibrational analysis using density functional theory-continuum model calculations

1998

Glycine and alanine aminoacids chemistry in solution is explored using a hybrid three parameters density functional (B3PW91) together with a continuum model. Geometries, energies, and vibrational spectra of glycine and alanine zwitterions are studied at the B3PW91/6-31+G∗∗ level and the results compared with those obtained at the HF and MP2/6-31+G∗∗ levels. Solvents effects are incorporated by means of an ellipsoidal cavity model with a multipolar expansion (up to sixth order) of the solute’s electrostatic potential. Our results confirm the validity of the B3PW91 functional for studying aminoacid chemistry in solution. Taking into account the more favorable scaling behavior of density funct…

Organic solvent desorption from two tegafur polymorphs.

2013

Desorption behavior of 8 different solvents from α and β tegafur (5-fluoro-1-(tetrahydro-2-furyl)uracil) has been studied in this work. Solvent desorption from samples stored at 95% and 50% relative solvent vapor pressure was studied in isothermal conditions at 30 °C. The results of this study demonstrated that: solvent desorption rate did not differ significantly for both phases; solvent desorption in all cases occurred faster from samples with the largest particle size; and solvent desorption in most cases occurred in two steps. Structure differences and their surface properties were not of great importance on the solvent desorption rates because the main factor affecting desorption rate …

Polychromatic femtosecond fluorescence studies of metal–polypyridine complexes in solution

2011

Femtosecond-resolved broadband fluorescence studies are reported for[ M(bpy)(3)](2+) (M = Fe, Ru), RuN3 and RuN719 complexes in solution. We investigated the pump wavelength dependence of the fluorescence of aqueous [ Fe(bpy)(3)](2+) and the solvent and ligand dependence of the fluorescence of Ru-complexes excited at 400 nm. For all complexes, the (MLCT)-M-1 fluorescence appears at zero time delay with a mirror-like image with respect to the absorption. It decays in <= 30-45 fs due to intersystem crossing to the (MLCT)-M-3 states, but a longer lived component of similar to 190 fs additionally shows up in RuN719 and RuN3. No solvent effects are detected. The very early dynamics are character…

Enthalpic and entropic contributions of water molecules to the functional T → R transition of human hemoglobin in solution

1992

Generalized solvent-mediated forces contribute to free energy at the functional T → R transition of human hemoglobin A (HbA). Their contribution is here sorted out quantitatively in both its enthalpic and entropic parts, along with the average number of water molecules involved. The latter (about 75 waters in average) must be considered together with HbA as one statistically defined functional unit for oxygen transport. Their configurations are expected to undergo frequent structural rearrangements. Lifetimes of statistically relevant configurations do not need to (although, of course, they may) exceed by more than a factor 5 the normal H-bond lifetimes of the pure solvent. Compared to the …

Calculation of the relative basicities of methylamines in solution

1990

Abstract The relative basicities in solution of the methylamines have been calculated using the model of Miertus, Scrocco and Tomasi to describe the solvent effect. The surface of the cavity is defined with the GEPOL method. The ab initio calculations have been performed using a 4-31G basis set. The relative order is reproduced using a combination of the gas-phase proton affinities obtained with quantum-mechanical methods by Eades, Weil, Dixon and Douglass and the solvation values obtained by us. The results seem to point out that the irregular order is not due to solvent but to basis-set effects.