• Bulletin of the Korean Chemical Society
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• 제3권1호
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• pp.9-13
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• 1982

Sulfametrole, $C_9H_{10}N_4O_3S_2$, crystallizes in the monoclinic system, space group $P2_1/n$ , with a = 8.145(2), b = 16.505(4), c = 9.637(1)${\AA},{\beta}=103.72(1)^{\circ},D_m=1.52gcm^{-3}$,Z=4.Intensities for 3594(2143 observed) unique reflections were measured on a four-circle diffractometer with Mo $K{\alpha}$ radiation $({\lambda}=0.71069{\AA})$. The structure was solved by direct method and refined by full-matrix least squares to a final R of 0.070. The geometrical features of the thiadiazole ring indicate some ${pi}$-electron delocalization inside the ring. The least squares planes defined by the benzene and thiadiazole rings are nearly perpendicular to each other(dihedral angle; $93.9^{\circ}$ ). All the potential hydrogen-bond donor atoms in the molecule, N(1) and N(2), are included in the hydrogen bonding. The molecules through hydrogen bonding form three dimensional network.

• Bulletin of the Korean Chemical Society
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• 제15권11호
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• pp.933-939
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• 1994

Using an atom superposition and electron delocalization molecular orbital (ASED-MO) method, we have investigated the vibrational and chemisorptive properties of adsorbates on a Pt(100) surface during CO oxidation. The calculated vibrational stretching frequency for a predicted structure of $[CO{\cdot}{\cdot}{\cdot}O]^*$ complex is 1642 $cm^{-1}$. The CO bond stretches by 0.05 ${\AA}$ when adsorbed on one-fold site, and is tilted by 30 ${\AA}$ from the surface normal. We find the decrease in CO vibrational frequency on going from the one-fold to the high coordination sites. Binding at the two-fold site is predicted to be favored for $Pt_{18}(100)$ and at the 1-fold site for $Pt_{23}(100)$. From the calculations of the steric interactions, we have found that pre-adsorbed oxygen modifies the surface so that CO is adsorbed on the one-fold site ordered in a $(\sqrt{2}{\times}{\sqrt}{2})R45^{\circ}$. Our results are in good agreement with recent experimental findings of Hong et al. [J.Phys. Chem. 1993, 97, 1258].

• Bulletin of the Korean Chemical Society
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• 제16권11호
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• pp.1028-1032
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• 1995

The structure and electronic properties of the Si(100) surface is studied using the atom superposition and electron delocalization method. The energy released when the symmetric dimer surface is reconstructed to form the buckled dimer surface with p(2X2) symmetry is calculated to be 0.99 eV per dimer in the case of ideal clean surfaces. This indicates that the surface dimer buckling is intrinsic from the viewpoint of thermodynamics. The relaxation energy, when water is adsorbed on the clean symmetric dimer surface to form the buckled dimer surface, is 2.25 eV per dimer for appropriate coverages. These results show that H2O molecule could induce a reconstruction of the surface structure through adsorption. The buckling of the surface dimer is, therefore, more favorable under the existence of water vapour. This conclusion supports the recently obtained experimental observations by Chander et al.

• Bulletin of the Korean Chemical Society
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• 제16권12호
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• pp.1176-1179
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• 1995

1H NMR spectra of pyridine, α-, β-, and γ-picoline coordinated to the paramagnetic heteropolyanion [Ni3(PW9O34)2]12- (P2Ni3) are reported. NMR lines are assigned to [Ni3(ptl)n(PW9O34)2]12- (n=1, 2 or 3; ptl=pyridine-type ligand) on the basis of their [P2Ni3]/[ptl] dependence. The formation constants for γ-picoline complexes at 25 ℃ are K1=80, K2=610, and K3=190 L mol-1. The monopicoline complex has greater affinity for γ-picoline than P2Ni3. A degradation product, [Ni2(WO2)(PW9O34)2]12-, was also identified at low pH by measuring the NMR spectrum of pyridine coordinated to it. The isotropic NMR shifts come mainly from the contact interaction due to σ-electron delocalization.

• Bulletin of the Korean Chemical Society
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• 제21권3호
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• pp.300-304
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• 2000

The B3LYP method based on the density functional theory(DFT) is shown to be much better than the ab initio MP2 method for structural determination of diphosphadithiatetrazocine systems having transannular S--S bonding. The presence of bonding between the two sulfur atoms across the cyclic ring is theoretically confirmed in the case of the neutral diphosphadithiatetrazocine. The S--S dobding disappears in the ionized species. The planarity of the dicationic heterocyclic ring system turns out to be closely associated with the $\pi-electron$ delocalization over the entire ring as well as the N-S-N bonds, which become stiffened upon ionizaiton. In the case of dianionic species, the chair-boat and chair conformers are nearly degenerate and far more stable than the crown conformer.

• Macromolecular Research
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• 제17권12호
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• pp.1003-1009
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• 2009

Copolymers of N-vinylpyrrolidone (NVP) comonomer with styrene (St), hydroxypropyl methacrylate (HPMA) and carboxyphenyl maleimide (CPMI) were synthesized by free radical polymerization using 2,2'-azobisisobutyronitrile (AIBN) initiator in 1,4-dioxane solvent. The copolymers formed were characterized by FTIR, $^1H$ NMR and $^{13}C$ NMR techniques and their thermal properties were studied by DSC and TGA. Copolymer composition was determined by $^1H$ NMR and/or by elemental analysis and monomer reactivity ratios (MRR) were estimated by the linear methods of Kelen-Tudos (K-T) and extended Kelen-Tudos (EK-T) and the non-linear approach. Copolymers of St and HPMA with NVP formed blocks of one of the monomer units, whereas alternating copolymers were obtained in CPMI-NVP, depending upon the side chain substitution. The MRR values are discussed in terms of monomer structural properties such as electronegativity and electron delocalization. The sequence distribution of monomers in the copolymers was studied by statistical method based on the average reactivity ratios obtained by EK-T method.

• 대한화학회지
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• 제37권10호
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• pp.895-902
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• 1993

란탄나이드 3가($Pr^{3+}$ 와 $Dy^{3+}$)와 유기 리간드를 (phen', terpy') 착물들의 거동을 UV/vis 분광분석, 자기화 그리고 전기화학적 방법에 의해 조사하였다. 착물들의 결정장 갈라짐 에너지 크기와 짝지움에너지 그리고 스핀상태는 착물들의 스펙트라로부터 얻었다. 이들 착물들에 대한 전지화학적 거동은 비수용매속에서 순환 전압전류법에 의해 관찰하였다. 이들 환원피크는 전자 전이에 의한 비가역적인 2단계의 환원 과정이었다.

• 대한화학회지
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• 제36권3호
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• pp.345-350
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• 1992

Ln$(NO_3)_3$/DMF 상자성 용액의 양성자 선-나비와 화학적이동을 240 K부터 380 K 사이에서 측정하였다. 이들 데이터로부터 DMF 분자의 CHO기에 대한 배위구 교환속도와 열역학 교환파라미터를 추출하였다. 1/$T_2$ 와 ${\Dellta}{\omega}$ 데이터의 온도의존성을 자세하게 분석하고 고찰하여 결과를 정리하였다. 분석의 결과를 살펴보면 짝짓지 않은 전자 스핀이 몇몇 $Ln^{3+}$이온에서 첫 배위구를 넘어 퍼지면서 bulk 용매의 DMF 분자로 스칼라이완의 기여를 제공하는 것 같다.

• Bulletin of the Korean Chemical Society
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• 제19권7호
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• pp.733-737
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• 1998

Using an atom superposition and electron delocalization molecular orbital (ASED-MO) method, we have compared adsorption properties of adsorbates on the Pt(Ill) surface with the Pt(lll)/γ-Al203 surface in the ethylene hydrogenation reaction. In two-layer thick model systems, the calculated activation energy of the hydrogenation by the surface platinum hydride is equal to the energy by the hydride over supported platinum/γ-alumina. The transition structure on platinum is very close to the structure on the supported platinum/γ-alumina surface. Hydrogenation by the surface hydride on platinum can take place easily because the activation energy is about 0.5 eV less than hydrogenation by ethylidene. On supported platinum/,y-alumina the activation energy of the hydride mechanism is about 0.61 eV less than that of ethylidene mechanism. In one-layer thick model systems, the activation energy of hydrogenation by ethylidene is about 0.13 eV less than the activation energy of hydride reaction. The calculated activation energy by the hydride over the supported platinum y-alumina is 0. 24 eV higher than the platinum surface. We have found from this result that the catalytic properties of one-layer thick model systems have been influenced by the support but the two-layer thick model systems have not been influenced by the support.

• Bulletin of the Korean Chemical Society
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• 제10권6호
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• pp.591-595
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• 1989

The$^{13}C$ NMR shifts of a series of para-substituted 9-aryl-tricyclo$[3.3.1.0^{2,8}]$non-9-yl and 8-aryl-tetracyclo$[3.2.1.0^{2,7}.0^{4,6}]$-oct-8-yl cations were measured in $FSO_3H/SO_2ClF \;at\; -90^{\circ}C\; or\; -70^{\circ}C$ in order to examine whether the ${\rho}^{c+}$ values can be used to explain the mechanism for the stabilization of the geometrically rigid cyclopropylcarbinyl cations. Plots of the ${\Delta}{\delta}^{c+}$ shifts against ${\sigma}^{c+}$ reveal excellent linear correlation. The tricyclononyl systems yield a ${\rho}^{c+}$ value of -4.95 with a correlation coefficient r = 0.9948. The tetracyclo-octanyl systems give a ${\rho}^{c+}$ value of -6.39 with r = 0.9943. A fair parallelism exists between the results of $^{19}F$ nmr studies and the change of ${\rho}^{c+}$ values in these cations. Accordingly, the present study established that the ${\rho}^{c+}$ value can be used as a mearsure of the geometric influence for the charge delocalization in cyclopropylcarbinyl cations.