• Bulletin of the Korean Chemical Society
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• 제32권6호
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• pp.1873-1878
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• 2011

Under solvent-free conditions and in one-pot, a series of 2-amino-4-aryl-3-cyano-6-(3,4-dimethoxyphenyl)-pyridines and 4-aryl-3-cyano-6-(3,4-dimethoxyphenyl)-2(1H)-pyridinones were prepared using 3,4-dimethoxyacetophenone, an aldehyde, malononitrile (or ethyl cyanoacetate), and ammonium acetate in the presence of 3-methyl-1-(4-sulfonylbutyl)imidazolium hydrogen sulfate $[HO_3S(CH_2)_4MIM][HSO_4]$ (a Br${\o}$nsted acidic ionic liquid) as the catalyst in very short reaction time. The preference for the formation of more stable tautomers was consistence with the theoretical calculation using the Gaussian 03 program at the B3LYP hybrid density functional level.

• Bulletin of the Korean Chemical Society
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• 제34권2호
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• pp.465-469
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• 2013

Proton transfer reaction is one of the most fundamental processes in chemistry and life science. Excited state intramolecular proton transfer (ESIPT) has been studied as a model system of the proton transfer, since it can be conveniently initiated by light. We report ESIPT reaction dynamic of 1-hydroxy-anthraquione (1-HAQ) in solution by highly time-resolved fluorescence. ESIPT time of 1-HAQ is determined to be $45{\pm}10$ fs directly from decay of the reactant fluorescence and rise of the product fluorescence. High time resolution allows observation of the coherent vibrational wave packet motion in the excited state of the reaction product tautomer. The coherently excited vibrational mode involves large displacement of the atoms, which shortens the distance between the proton donor and the acceptor. With the theoretical analysis, we propose that the ESIPT of 1-HAQ proceeds barrierlessly with assistance of the skeletal vibration, which in turn becomes excited coherently by the ESIPT reaction.

• Bulletin of the Korean Chemical Society
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• 제29권11호
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• pp.2252-2258
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• 2008

• Bulletin of the Korean Chemical Society
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• 제30권7호
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• pp.1667-1670
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• 2009

• 한국세라믹학회지
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• 제47권1호
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• pp.39-46
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• 2010

The kinetics of cation reequilibration have been studied theoretically and experimentally in complex oxides after an external perturbation of equilibrium by temperature jumps. A general kinetic model for cation redistribution amongst non-equivalent sites in complex oxides is derived based on a local homogeneous point defect mechanism involving cation vacancies. Temperature-jump optical relaxation spectroscopy has been established to investigate cation kinetic processes in spinels and olivines. The kinetic model satisfactorily describes the experimental absorbance relaxation kinetics in cobalt containing olivines and in nickel containing spinels. It is found that the kinetics of cation redistribution in complex oxides shows a strong temperature- and composition-dependence. Activation energies for cation redistribution in Co-Mg olivines are found to range between 200 and 220 kJ/mol whereas an energy barrier of about 230 kJ/mol is observed in the case of nickel gallate spinel.

• Bulletin of the Korean Chemical Society
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• 제2권1호
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• pp.24-28
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• 1981

Theoretical studies of the sodium cation binding and the isotope hydration effects on the static model compound B-DNA have been qualitatively elucidated by using empirical potential energy functions. In the first place, the sodium cations bound to phosphate anions and their hydration scheme have been optimized and have given a reasonable agreement with other theoretical results and experimental studies. In the second stage, the isotope effect on the hydration through the substitution of $D_2O\;for\;H_2O$ has been carried out by the same procedure. The stabilization of B-DNA has been explained and compared in terms of the sodium cation binding to phosphate anions and its hydration in both cases of $H_2O\;and\;D_2O$.

• Bulletin of the Korean Chemical Society
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• 제30권10호
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• pp.2233-2239
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• 2009

In the present study, firstly, the variations of the geometric parameters induced by different substituents on boroxine skeleton (symmetrically H, $CH_3$, Cl, F, $NO_2$ substituted boroxines) are investigated by using B3LYP/6-31G(d,p), RHF/6-31G(d,p), and MP2/6-31G(d,p) levels of the theory. The second objective is to estimate the substituent effect on the molecular aromaticity of boroxine derivatives using energetic and NICS criteria. Moreover, the effects of different theoretical levels on NICS values have been investigated in a systematic approach. Lastly, a rotational analysis has been performed to investigate the effect of rotation around the B-Me and B-$NO_2$ bonds on total energy of the system. It has been found that electron withdrawing substituents contribute the aromaticity of boroxine affirmatively. Conversely, electron donors make the system less aromatic. Also, the theoretical vibrational spectra for these boroxine derivatives are presented and compared with the experimental data from the literature.

• 대한화학회지
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• 제63권3호
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• pp.160-165
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• 2019

A series of reactions between an amino alcoholic ligand, cis-2-((2-((2-hydroxyethyl)amino)ethyl)amino)cyclohexan-1-ol (HEAC), with the mixtures of group 12 metals including, $HgCl_2/CdCl_2$, $HgCl_2/CdI_2$, $ZnCl_2/CdCl_2$ and $ZnCl_2/CdCl_2/HgCl_2$ was experimentally and theoretically studied to determine the most stable product of these reactions. Furthermore, the Cambridge Structural Database (CSD) studies were done to evaluate the theoretical results. The products were characterized by elemental analysis, FT-IR, Raman, $^1H$ NMR spectroscopy and single-crystal X-ray diffraction. Based on these investigations a binuclear structure of cadmium, [$Cd_2(HEAC)_2({\mu}-Cl)_2Cl_2$] (1), is the most stable product that was formed in all studied reactions between HEAC and metals mixtures. In this structure, the cadmium atom has a $CdN_2O({\mu}-Cl)_2Cl$ environment and distorted octahedral geometry.

• Macromolecular Research
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• 제8권6호
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• pp.292-297
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• 2000

The theoretical synthesis of the isotactic and syndiotactic poly(methyl methacrylate) were carried out as a model for real polymerization reactions following the normal chain reaction processes by repeating the uniform localization of wave functions with inclusion of the interaction between the end group of the cluster and an attaching molecule by the elongation method, and then, the calculated value was compared with the usual PM$_3$ calculation. The results revealed that a reaction of cluster with monomer molecules has made it possible to calculate the electronic structure and total energy of polymer with nearly infinite length and a matrix of constant dimension. The isotactic poly(methyl methacrylate) is more stable than syndiotactic one. The same tendency have been found between the experimentally measured properties and a calculated total energy to explain the chain motion in isotatic and syndiotactic poly(methyl methacrylate).

• Bulletin of the Korean Chemical Society
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• 제32권3호
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• pp.889-893
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• 2011

The energetics and transition state (TS) structures of the reactions of six substrates, $R_1R_2P$(=O or S)Cl-type where $R_1=R_2$=Me and/or MeO, with ammonia in acetonitrile are theoretically investigated at the level of CPCM-MP2/6-31+G(d) and CPCM-MP2/6-311+G(3df,2p). The degrees of distortion of TS from the ideal trigonal bipyramidal pentacoordinate, ${\Delta}{{\delta}}_{{\neq}b}$ for a backside and ${\Delta}{{\delta}}_{{\neq}f}$ for a frontside attack, are calculated. The results of calculation suggest that the feasibility of a frontside attack for P=S is greater than that for P=O system when the two ligands, $R_1$ and $R_2$, becomes larger. The experimental and calculated results of anilinolyses of $R_1R_2P$(=O or S)Cl-type show the consistent tendencies.