• Bulletin of the Korean Chemical Society
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• v.19 no.9
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• pp.897-906
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• 1998

A new synthesis has been developed for 1-thia-4,7-diazacyclononane and the complexation behavior of a particular derivative has been explored. The pentadentate ligand 4,7-bis(2-pyridylmethyl)-l-thia-4,7-diazacyclononane ([9]$N_2SPY_2$) and its iron(Ⅱ) and manganese(Ⅱ) complexes were prepared and characterized. Magnetic moments of 5.17 and 5.90 μB respectively, indicate that the iron(Ⅱ) and manganese(Ⅱ) complexes are high spin. Charge transfer transitions (d-π*) occur for [Fe(Ⅱ)([9]$N_2SPY_2)(X)]^{n+}$at 27027, 25000, and 24390 cm-1 for X=$H_2O$, Cl-, and OH-, respectively. In acetonitrile solution, the cyclic voltammogram of the manganese(Ⅱ) complex exhibits a redox couple at 0.92 V vs. NHE while the redox potentials for [Fe(Il)([9]$N_2SPY_2)(X)]^{n+}$ are 0.70, 0.66, and 0.37 V vs. NHE for X=$H_2O$, Cl-, and OH-, respectively. The d-π* charge transfer energy and Fe(Ⅱ)/Fe(Ⅲ) redox potential for [Fe(Ⅱ)([9]$N_2SPY_2)(X)]^{n+}$ increase in the same order: $H_2O>Cl^- >OH^-$. The crystal structures of the iron(Ⅱ) and manganese(Ⅱ) complexes reveal that the metal ions are sixcoordinate, binding to four nitrogen atoms and a sulfur atom from the pentadentate ligand, as well as a chloride anion, with the chloride and sulfur atoms in cis positions. The two metals have similar coordination geometries, which are closer to trigonal prismatic than octahedral. In both iron and manganese complexes, the M-N($sp_3$) trans to Cl- is 0.07 Å longer than the one cis to Cl- , and M-N($sp^2$) trans to S is 0.05 longer than the one cis to S atom.

• Journal of the Korean Chemical Society
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• v.29 no.4
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• pp.372-381
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• 1985

Oxo molybdenum (V) complexes of substituted 8-quinolinols were synthesized and characterized by means of the investigation of elemental analysis, infrared spectra, electron spectra, electric conductivity and mass spectrometry compared with oxo molybdenum (VI) complexes. Oxo molybdenum(V) complexes were nonelectrolyte and one strong band of stretching mode of molybdenum and terminal oxygen appeared approximately $940cm^{-1}$. Oxo molybdenum(VI) complexes gave two peaks corresponding molybdenum containing ions, a molecular ion (I) of a 2 : 1 (ligand : metal) chelate and a fragment ion (II) of a 1:1 chelate due to the loss of ligand radical from ion (I). Molybdenum(V) complexes were observed the fragment ion(II) of a 1 : 1 chelate partly. The electronic spectra corresponding to d-d transition and charge transfer transition were observed and interpreted.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.220-220
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• 2016

본 연구에서는 녹황색 빛을 내는 NaY(WO4)2:Tb3+ 형광체 파우더를 하소 350도에 1시간 소결 950도에 4시간 고상반응법으로 합성하였으며, 파우더는 X-ray diffraction과 PL 장비를 이용하여 측정하였다. XRD 분석은 Tb3+이온 도핑농도에 의한 순수한 NaYWO4 상을 나타내었다. Fig.1 220-330nm에서 관찰되는 넓은 밴드는 $O2-{\rightarrow}W6+$에 의해 발생한 LMCT(ligand to metal charge transfer)이고, Tb3+에서 WO42-그룹으로 에너지 전달에 의해서 생긴다. 이것의 최대세기는 272nm 이다. LMCT 옆 330-390nm에 관찰되어지는 약한 강도와 넓은 밴드는 Tb3+ 4f8의 f-f transition에 의해 발생한다. Fig.2에서 보여 지듯이$ 5D4{\rightarrow}7F6$, 7F5, 7F4, 7F3는 파장 489nm, main peak인 545nm (Green,초록색), 588nm (orange, 주황색), 620nm (Red, 적색)에서 Peak가 나타났으며, Tb3+이온의 함량비가 0.08mol일 때 최대 발광이 관측 되었다.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2013.05a
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• pp.161-161
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• 2013

본 연구에서는 백금 나노입자의 크기, 형상, 분포도에 따른 전기 화학적 효율을 평가하기 위해 계면활성제 농도를 달리하여 백금 나노입자를 합성하였다. 계면활성제로는 CTAB(cetyltrimethylammonium bromide)이 사용되었으며, 0.5 mM의 $H_2PtCl_6$의 백금 염을 환원시키기 위하여 유체 플라즈마 공정을 이용하였다. 공정 시간은 UV-vis 스펙트럼 결과를 토대로, 262 nm의 파장대에서 관찰된 LMCT(ligand-to-metal charge transfer) peak이 사라지는 시간을 기준으로 하여 공정을 진행하였다. 합성된 나노입자는 순환 전류-전압곡선(CV), TEM이미지와 XRD 분석을 이용하여 전기화학적 특성, 입자의 평균 크기 및 형상 변화를 비교 분석 하였다. 그 결과 CTAB을 넣지 않은 백금나노입자의 경우, CTAB을 넣고 제조한 백금 나노입자와는 달리 구의 형태로 뭉쳐있음을 관찰하였고, 이러한 백금 나노입자의 구조는 보다 높은 전기화학적 활성 특성을 가짐을 보였다.

• Journal of the Korean Chemical Society
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• v.39 no.8
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• pp.611-616
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• 1995

Oxovanadium(IV) complexes with salicylaldoxime, o-vanilline oxime, 2-hydroxy-4-methoxybenzaldoxime, 2-hydroxy-5-methoxybenzaldoxime and 2-hydroxy-5-nitrobenzaldoxime were synthesized. The complexes have been characterized by elemental analysis, electric conductivity measurement, infrared spectrometry, electronic spectrometry, mass spectrometry, and thermal analysis. The results of elemental analysis were well coincided with the theoretical values. The values of molar conductance of the complexes in DMF implicated that the complexes were non-electrolyte. The characteristic stretching frequency of V=O appeared strong band in the range of $980{\pm}20\;cm^{-1}.$ All the complexes showed two d-d transition in visible spectra and two charge transfer transitions in ultraviolet spectra. Results of mass spectrometry of $VO(sal)_2\;and\;VO(van)_2$ indicated two peaks corresponding to vanadium containing ion(I) of 1 : 2(metal to ligand) chelate and a fragment ion(II) of 1 : 1 chelate due to loss of ligand radical from ion(I). The thermal analysis showed the endothermic peak due to the thermal decomposition.

• Bulletin of the Korean Chemical Society
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• v.29 no.3
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• pp.546-550
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• 2008

The title compound of nicotinato lead(II) complex [Pb$(C_5H_4NCOO)_2$] has been optimized at B3LYP/LANL2DZ and HF/LANL2DZ levels of theory. The calculated results show that the lead(II) ion adopts 2- coordinate geometry, which is the same as its crystal structure and different from the 4-coordinate geometry of isonicotinato lead(II) complex. Atomic charge distributions indicate that during forming the title compound, each nicotinic acid ion transfers their negative charges to central lead(II) ion. The electronic spectra calculated by B3LYP/LANL2DZ level show that there exist two absorption bands, which have some red shifts compared with those of isonicotinato lead(II) complex and the electronic transitions are mainly derived from intraligand $\pi$ -$\pi$ transition and ligand-to-metal charge transfer (LMCT) transition. CIS-HF method is not suitable for the system studied here. The thermodynamic properties of the title compound at different temperatures have been calculated and corresponding relations between the properties and temperature have also been obtained. The second order optical nonlinearity was calculated, and the molecular hyperpolarizability was $1.147754{\times}10^{-30}$ esu.

• Bulletin of the Korean Chemical Society
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• v.31 no.6
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• pp.1615-1620
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• 2010

Bis-[dipyrido[3,2-$\alpha$:2',3'-c]phenazine)$_2$(1,10-phenanthroline)$_2Ru_2$]$^{2+}$ complexes (bis-Ru(II) complexes) tethered by linkers of various lengths were synthesized and their binding properties to DNA investigated by normal absorption and linear dichroism spectra, and fluorescence techniques in this study. Upon binding to DNA, the bis-Ru(II) complex with the longest linker (1,3-bis-(4-pyridyl)-propane), exhibited a negative $LD^r$ signal whose intensity was as large as that in the DNA absorption region, followed by a complicate $LD^r$ signal in the metal-to-ligand charge transfer region. The luminescence intensity of this bis-Ru(II) complex was enhanced. The observed $LD^r$ and luminescence results resembled that of the [Ru(1,10-phenanthroline)$_2$ dipyrido[3,2-$\alpha$:2',3'-c]phenazine]$^{2+}$ complex, whose dipyrido[3,2-$\alpha$:2',3'-c]phenazine (dppz) ligand has been known to intercalate between DNA bases. Hence, it is conclusive that both dppz ligands of the bis-Ru(II) complex intercalate. The binding stoichiometry, however, was a single intercalated dppz per ~ 2.3 bases, which violates the "nearest binding site exclusion" model for intercalation. The length between the two Ru(II) complexes may be barely long enough to accommodate one DNA base between the two dppz ligands, but not for two DNA bases. When the linker was shorter (4,4'-bipyridine or 1,2-bis-(4-pyridyl)-ethane), the magnitude of the LD in the dppz absorption region, as well as the luminescence intensity of both bis-Ru(II) complexes, was half that of the bis-Ru(II) complex bearing a long linker. This observation can be elucidated by a model whereby one of the dppz ligands intercalates while the other is exposed to the aqueous environment.

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2056-2062
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• 2013

The dihydroxy naphthalene/$TiO_2$ complexes with different substitution patterns were prepared by surface modification. X-ray diffraction, UV-Vis spectroscopy, photoluminescence, and X-ray photoelectron spectroscopy were used to characterize the prepared composite materials. The results indicated that the surface modification did not influence the crystallization of $TiO_2$. The visible-light absorbances of prepared dihydroxy naphthalene/$TiO_2$ complexes could be assigned to the ligand-to-metal charge transfer. The obtained catalyst exhibited outstanding photocatalytic activity and stability under visible light. A linear relationship existed between the percentages of hydroxynaphthalenes coordinated on $TiO_2$ surface and $H_2$ production ability. The substitution pattern of dihydroxy naphthalene and $CH_3OH$ content could also influence the photocatalytic performance remarkably. The photocatalytic $H_2$ production ability was further improved after loading with ultra low concentration of Pt, 0.02 wt %. The possible mechanism was proposed.

• Bulletin of the Korean Chemical Society
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• v.18 no.7
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• pp.743-749
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• 1997

Local structure refinement of the BaFe1-xSnxO3-y system (x=0.00-0.50) has been carried out with Fe K-edge x-ray absorpion spectroscopic studies. It is found out that the Fe ions are placed in two different symmetric sites such as tetrahedral and octahedral sites in the compounds by comparison with Fe K-edge x-ray absorption near edge structure (XANES) spectrum of the γ-Fe2O3 compound as a reference. Small absorption peaks of dipole-forbiden transitions appear at a pre-edge region of 7111 eV due to the existence of Fe ions in the tetrahedral and octahedral sites. The peak intensity decreases with the substitution amount of Sn ion. Three different absorption peaks of 1s→4p dipole-allowed transition appear on the energy region between 7123 and 7131 eV. The peaks correspond to 1s→4p main transition of Fe ions in tetrahedral and octahedral sites and 1s→4p transition followed by the shakedown process of ligand to metal charge transfer. The bond distances between Fe ions in the tetrahedral site and nearest neighboring oxygen atom (Fe-4O), and those in octahedral site (Fe-6O) are determined with the extended x-ray absorption fine structure (EXAFS) analysis. Two different interatomic distances increase with the substitution amount of Sn ion and also the bond lengths of Fe-4O are shorter than those of Fe-6O in all compounds.

• Bulletin of the Korean Chemical Society
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• v.32 no.7
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• pp.2358-2368
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• 2011

Density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations, employing the B3LYP method and the LANL2DZ, 6-31G$^*$(LANL2DZ for Tc), 6-31G$^*$(cc-pVDZ-pp for Tc) and DGDZVP basis sets, have been performed to investigate the electronic structures and absorption spectra of the technetium-99m-labeled methylenediphosphonate ($^{99m}Tc$-MDP) complex of the simplest diphosphonate ligand. The bonding situations and natural bond orbital compositions were studied by the Mulliken population analysis (MPA) and natural bond orbital (NBO) analysis. The results indicate that the ${\sigma}$ and ${\pi}$ contributions to the Tc-O bonds are strongly polarized towards the oxygen atoms and the ionic contribution to the Tc-O bonding is larger than the covalent contribution. The electronic transitions investigated by TDDFT calculations and molecular orbital analyses show that the origin of all absorption bands is ascribed to the ligand-to-metal charge transfer (LMCT) character. The solvent effect on the electronic structures and absorption spectra has also been studied by performing DFT and TDDFT calculations at the B3LYP/6-31G$^*$(cc-pVDZ-pp for Tc) level with the integral equation formalism polarized continuum model (IEFPCM) in different media. It is found that the absorption spectra display blue shift in different extents with the increase of solvent polarity.