Search results for "Function"
showing 10 items of 14432 documents
Toward an understanding of the selectivity in domino reactions. A DFT study of the reaction between acetylenedicarboxylic acid and 1, 3-Bis(2-furyl)p…
2000
The mechanism of the domino reaction between acetylenedicarboxylic acid and 1,3-bis(2-furyl)propane has been theoretically studied in the framework of density functional theory. This domino process comprises two consecutive cycloaddition reactions: the first one is initialized by the nucleophilic attack of the C5 position of the furan ring to a conjugate position of acetylenedicarboxylic acid to give a zwitterionic intermediate, which by a subsequent ring-closure process affords an oxanorbornadiene intermediate. The second reaction is an intramolecular concerted cycloaddition of this intermediate to give the final dioxapentacyclic adduct. For the second cycloaddition, which corresponds to t…
Novel Applications of Dynamic NMR in Organic Chemistry
2004
Abstract This review article is oriented on NMR applications in studying various dynamic processes of organic molecules. The topic as a whole is too large to be covered exhaustively in one article or by one author. Therefore, the literature searches are limited mainly for the years 1999–2001. Further, many interesting branches joined essentially with organic chemistry such as supramolecular and organometallic chemistry are left outside this article because there exist recent reviews on these topics. Similarly, the theoretical background of dynamic NMR is not included. The nature of dynamic NMR itself is changing with the recent progress in computational possibilities to estimate the differe…
Localized states in wide-gap oxide glasses
1997
Localized states manifest themselves by light absorption at the optical gap of a glass and by luminescence excited there with Stoke's shift. They are created by the minority structural motifs of one or many structural modifications in which a material can exist, and which can provide electronic states absorption at the optical gap. Their wavefunctions overlapping determine the luminescence intensity dependence on the temperature [I(T)on the order of magnitude exp(- T/T 0 )] and power law (t -1 ) of luminescence decay kinetics, which include intra-center processes due to triplet-singlet transitions and recombination processes due to a tunnel and overbarrier transitions, as well as a fast com…
1,3-Di(hetero)aryl-7-substituted Pyrenes—An Undiscovered Area of Important Pyrene Derivatives
2019
Despite the pyrene derivatives have been covered extensively by scientists during the last years, many interesting properties and applications of pyrene derivatives have been presented, nowadays there are still areas of pyrenes’ chemistry that need to be fulfilled. Most of the described in literature pyrenes are 1,3,6,8-tetrasubstituted followed by 4,5,9,10-tetrasubstituted, 2,7-, and 1,6-, and 1,8-disubstituted pyrene derivatives. In the case of 1,3-di(hetero)aryl-7-substituted, there are only a few examples of derivatives containing at position 7 - tert-butyl group. In this work, the necessity of synthesis of 1,3-di(hetero)aryl-7-substituted pyrenes is presented based on the results of th…
Selectively Functionalized Constrained Polyazamacrocycles: Building Blocks for Multifunctional Chelating Agents
2013
A new class of cross-bridged and side-bridged 1,4,7,10-tetraazacyclotridecanes (homocyclens) bearing an aminomethyl pendant arm on the carbon skeleton has been prepared. The regioselectivity of the quaternization of the bis-aminal intermediates is discussed on the basis of X-ray diffraction and NMR experiments. These new polyazamacrocycles are valuable precursors of bifunctional chelating agents for applications in nuclear medicine.
A coupled cluster calculation of the spectrum of urea
2001
Several coupled cluster methods have been used to compute the vertical excitation energies and oscillator strengths of the lowest singlet states of urea. Except for one excitation, the results are in good agreement with experiment, but previously non-detected transitions have been found.
On the electron affinity of TCNQ
2004
The electron affinity of 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) has been studied with density functional theory and coupled cluster (CC) procedures. The adiabatic electron affinity of TCNQ calculated with the B3LYP method is about 1 eV higher than the available experimental value. At the CCSD(T) level, the theoretical result is overestimated by more than 0.4 eV. The electron affinity computed for TCNQ is larger than that obtained for tetracyanoethylene at all levels of calculation, exactly the opposite of what is observed experimentally. Accordingly, a call for an additional empirical measurement of such a property is made.
A dft study of the regioselectivity in intramolecular diels-alder reactions with formation of a tricyclodecane skeleton
2011
Three different intramolecular Diels-Alder (IMDA) reactions associated with the formation of fused and bridged tricyclodecane skeletons have been studied at the B3LYP/6-31G(d) computational level. While substitution on the diene and dienophile fragments modulates the polar character of the reaction, the strain effect produced by the methylene tether affects the activation energy, and its torsion controls the different regioisomeric channels of the IMDA process. Analysis of the reactivity indices recently proposed (J. Soto-Delgado et al., Org. Biomol. Chem., 2010, 8, 3678) within the conceptual density functional theory allows for the characterization of the mechanism including the charge tr…
An Understanding of the Electrophilic/Nucleophilic Behavior of Electro-Deficient 2,3-Disubstituted 1,3-Butadienes in Polar Diels−Alder Reactions. A D…
2008
The electrophilic/nucleophilic behavior of dimethyl 2,3-dimethylenesuccinate 1, an electron-deficient 2,3-disubstituted 1,3-butadiene, in polar Diels-Alder reactions has been studied using DFT methods at the B3LYP/6-31G(d) level of theory. The electronic nature of bonding of the transition structures involved in the cycloaddition reactions of the diene 1 toward the nucleophilically activated dienophile 6 and the strong electrophilically activated dienophile 7 has been carefully examined within the natural bond orbital (NBO) and the topological analysis of the electron localization function (ELF) frameworks. Additionally, a study of the global electrophilicity pattern of the reagents at the …
ChemInform Abstract: A Theoretical Determination of the Dissociation Energy of the Nitric Oxide Dimer.
2010
Multi-reference CI methods have been applied to determine the dissociation energy and structure of thecis-N2O2 molecule. The convergence of the theoretical result has been checked with respect to a systematic expansion of the one-electron basis set and the multi-reference CI wave function. The best calculated value, 13.8 kJ/mol, is in agreement with the experimental value, 12.2 kJ/mol. It has been obtained with an extended ANO-type basis set [6s5p3d2f], including the effect of the basis set superposition error (BSSE) in the geometry optimization, and additional effects, such as the electron correlation of core electrons and relativistic corrections, using the average coupled pair functional…