• Bulletin of the Korean Chemical Society
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• v.13 no.3
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• pp.256-259
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• 1992

The 14-membered tetraaza macrocyclic ligand 1,8-diethyl-5,12-dimethyl-1,4,8,11-tetraazacyclote tradeca-4,11-diene(B) can be synthesized as its dihydroperchlorate salt by the one-pot reaction of 2-ethylaminoethylamine, methylvinyl ketone, and perchloric acid in absolute ethanol. The reaction of Ni(II) or Cu(II) ion and the salt yields $[M(B)]^{2+}$ (M = Ni(II) or Cu(II)), which reacts with $NaBH_4$ to produce $[M(D)]^{2+}$ (D = 1,8-diethyl-5,12-dimethyl-1,4,8,11-tetraazacyclote tradecane). The complexes $[M(L)]^{2+}$ (L = B or D) have planar geometry and contain two ethyl groups at the donor nitrogen atoms of the ligands. The red solids $[Cu(B)](X)_2(X)$ = $ClO_4-$ or $PF_6^-$) react with water molecules of atmospheric moisture to produce the purple solids in which water molecules are coordinated to the metal ion. Synthesis, characterization, and the properties of the new N-ethylated macrocyclic ligands and their Ni(II) and Cu(II) complexes are reported.

• Journal of the Korean Chemical Society
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• v.29 no.3
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• pp.226-232
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• 1985

Dioxomolybdenum(VI) complexes, MoO$_2$(H-Sal-R)$_2$, R; arylamines, have been synthesized by reactions of dioxobis (salicylaldehydato) molybdenum(VI) with various primary amines. These complexes have been characterized by electric conductivity and spectroscopic studies. Infrared, uv-vis, and proton nmr spectra show that the complexes are six-coordinated with cis-MoO$_2$ group. And mass spectra indicates that the combining ratios for Mo (VI)-ligand are 1 : 2. They are yellow, stable for a considerably long time in the atmosphere at room temperature and slightly soluble in alcohol, dichloromethane and dimethylformamide but insoluble in benzene, ether and carbon tetrachloride.

• Journal of the Korean Chemical Society
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• v.35 no.6
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• pp.645-652
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• 1991

The stability constants$(K_f)$ of the complexes of some transition and post-transition metal ions (Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Cd(Ⅱ), Pb(Ⅱ), Hg(Ⅱ)) with $N_2O_3$-donor macrocyclic ligand, 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane ($NtnOdienH_4$), have been determined by potentiometry in aqueous solution at $25^{\circ}C$. Log $K_f$ values of the complexes were : Co(Ⅱ): 3.83, Ni(Ⅱ) : 4.56, Cu(Ⅱ) : 7.74, Zn(Ⅱ) : 4.98, Cd(Ⅱ) : 3.91, Pb(Ⅱ) : 6.65, and Hg(Ⅱ) : 14.87. The order of stabilities of transition metal complexes was the same as the natural order of stability proposed by Williams-Irving. In post-transition metal complexes, the order of stabilities was Cd(Ⅱ) < Pb(Ⅱ) < Hg(Ⅱ), and the covalent character in metal ion-donor atoms bonds appeared a dominant factor in the stability. In methanol solution, each metal ion forms 1 : 1 complex, while Ni(Ⅱ) ion forms both 1 : 1 and 1 : 2 complexes. It was confirmed by $^1H-$ and $^{13}C-$NMR spectral study that the nitrogen atoms in the ligand were major contributors for the complexation of post-transition metal ions with the ligand. It was shown, by elementry analysis, electrical conductivity and magnetic susceptibility measurements, and spectral analysis, that solid Cu(Ⅱ)-and Zn(Ⅱ)-complexes have a distorted octahedral and a tetrahedral structure, respectively.

• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.679-682
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• 2009

Utilizing a planar five coordinating N3S2 ligand, 2,6-bis(2-methylthiophenyliminomethyl)pyridine, a pseudo 7-coordinated manganese(II) complex with two labile triflate anions in the axial positions was synthesized. The reaction of the manganese(II) complex with an oxidant, iodosylbenzene, produced a metastable high-valent manganese(IV)-oxo species at 0 ${^{\circ}C}$. The high-valent Mn(IV)-oxo intermediate was characterized with a UV-vis spectrophotometer and an electrospray ionization mass spectroscopy. Reactivity studies of the Mn(IV)=O species revealed that the intermediate is capable of oxygenating $PPh_3$ and N-dealkylating N,N-dimethyl-toludine.

• Bulletin of the Korean Chemical Society
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• v.27 no.11
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• pp.1752-1756
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• 2006

This study explores and interprets in a new way the complex solvent and the temperature dependence of the NMR shifts for the N-$CH_2$ protons in tris(N,N-diethyldithiocarbamato) iron(III) in acetone, benzene, carbon disulfide, chloroform, dimethylformamide and pyridine. The NMR shifts are interpreted in terms of the Fermi contact interaction and the dipolar term from the multipole expansion of the interaction of the electron orbital angular momentum and the electron spin dipolar-nuclear spin angular momentum. This analysis yields a direct measure of the effect of the solvent system on the environment of the transition metal ion. The results are analysed in terms of the crystal field environment of the transition metal ion with contributions from (a) the dithiocarbamate ligand (b) the solvent molecules and (c) the interaction of the effective dipole moment of the polar solvent molecule with the transition metal ion complex.

• Korean Journal of Crystallography
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• v.11 no.1
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• pp.28-33
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• 2000

The slow of 2,3-bis(2-pyridyl)pyarzine(bpp) with Ag(CF₃CO₂) produces crystalline product suitable for X-ray crystallography. Crystallographic characterization of the crystal (C/sub 32/H/sub 20/-F/sub 6/N/sub 8/O₄Ag₂: triclinic P1, a=8.518(5)Å, b=9.546(2)Å, c=10.632(1)Å, α=81.11(1)°, β=87.61(3)°, γ=75.66(3)°, V=827.5(5)ų, Z=1, R=0.0431) has provided that the complex is a cyclic dimer [Ag(bpp)(CF₃CO₂)]₂. Each bpp ligand connects two tetrahedral silver(I) ions in a tridentate mode (Ag-N, 2.26()-2.43(2)Å), and the trifluoroacetato anion is bonded to each silver(I) atom in a monodentate fashion (Ag-O, 2.38(1); 2.39(2) Å). The skeletal cyclic dimer is stable up to 212℃, and drastically decomposes around this temperature.

• Bulletin of the Korean Chemical Society
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• v.30 no.5
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• pp.1113-1117
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• 2009

The one-dimensional coordination polymers, $[Cu^{II}(L)(NO_3)_2]_n$ (1) and {$[Cu^{II}(L)(NO_3)]{\cdot}2H_2O}_{2n} (2), were synthesized from $Cu(NO_3)_2{\cdot}3H_2O$ and 2-[(pyridin-3-ylmethyl)amino]ethanol (L, PMAE) in methanol by controlling the molar ratio of copper(II) salt. Copper(II) ion in 1 has one pyridine group of PMAE whose an aminoethanol group coordinates adjacent copper(II) ion. As the pyridine group is bonded to neighboring copper(II) ion, 1 becomes a one-dimensional chain. Contrary to 1, the structure of 2 shows that the oxygen atom of ethoxide group is bridged between two copper(II) ions, which forms a dinuclear complex. Additionally, the pyridine group of PMAE included one dinuclear unit is coordinated to the other dimeric one each other, which leads to a one-dimensional polymer. Due to the structural differences, 1 exhibits weak antiferromagnetic interaction, while 2 shows strong antiferromagnetic interaction. Due to direct spin exchange via oxygen of PMAE 2 has a much strong spin coupling than 1.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2375-2380
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• 2013

Two metal-organic frameworks based on the connectivity co-effect between rigid benzenedicarboxylic acid and bridging ligand have been synthesized $[Zn_2(3-NO_2-bdc)_2(4,4'-bpy)_2H_2O]_n$ (1), $[Co(3-NO_2-bdc)(4,4'-bpy)H_2O]_n$ (2) (where $3-NO_2-bdcH_2$ = 3-nitro-1,2-benzenedicarboxylic acid, 4,4'-bpy = 4,4'-bipyridine). The two novel complexes were characterized by IR spectrum, elemental analysis, fluorescent properties, thermogravimetric analysis, single-crystal X-ray diffraction and powder X-ray diffraction (PXRD). X-ray structure analysis reveals that 1 and 2 are two-dimensional (2D) network structures. Complex 1 and complex 2 belong to triclinic crystal with P-1 space group. The luminescence measurements reveal that two complexes exhibit good fluorescent emissions in the solid state at room temperature. Also, thermal decomposition process and powder X-ray diffraction of complexes were investigated.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.1965-1969
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• 2014

A new tetranuclear Mn(III) complex $[Mn^{III}{_4}(sae)_4({\mu}_3-O)({\mu}_{1,1}-N_3)(OH)(H_2O)_2]{\cdot}H_2O$ (1) ($H_2sae$ = 2-salicylideneamino-1-ethanol) has been synthesized by the reaction of $MnCl_2{\cdot}4H_2O$, $H_2sae$ and sodium azide in the mixed solvent of methanol, acetonitrile and water. The X-ray diffraction analysis shows that the four Mn(III) ions in complex 1 have a unique adamantine arrangement, whereas the coordination environment of each Mn(III) ions is different. Magnetic studies indicate that complex 1 manifests antiferromagnetic behaviors. The magnetic susceptibilities of complex 1 have been fitted by two magnetic models based on the suitable analysis of its magnetic structural topology.

• Bulletin of the Korean Chemical Society
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• v.33 no.6
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• pp.1929-1933
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• 2012

Two cobalt(II) compounds $[Co(2,2{^\prime}-bipy)(H_2O)_2(SO_4)]_n$ (1) and $[Co_2(2,2^{\prime}-bipy)_2(btec)(H_2O)_6]{\cdot}2H_2O$ (2) (2,2'-bipy = 2,2'-bipyridine, $H_4btec$ = 1,2,4,5-benzenetetracarboxylic acid), have been simultaneously synthesized by a one-pot slow solvent evaporation reaction. Their structures were determined by single-crystal X-ray diffraction and further characterized by X-ray powder diffraction (XRPD), IR, elemental and thermogravimetric analysis (TGA). The structural analysis reveals that compound 1 exhibits an infinite 1D chain structure with the octahedral Co(II) centers bridging by the tetrahedral ${\mu}_2-SO{_4}^{2-}$ ligands, while compound 2 possesses a dinuclear $Co_2(2,2^{\prime}-bipy)_2(btec)(H_2O)_6$ unit and the two adjacent octahedral Co(II) ions are linked by the bismonodentately coordinated btec ligand. Additionally, compound 2 exhibits blue fluorescent emission in the solid state at room temperature.