• Journal of the Korean Chemical Society
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• v.57 no.3
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• pp.311-315
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• 2013

The geometry structures of hexa-coordinated [NiLX]X complexes ($X=Cl^-,\;Br^-,\;I^-$) {L = 8,9,18,19-tetrahydro-7H,17H-dibenzo[f,o] [1,5,9,13]dioxadiaza cyclohexadecine-8,18-diol} are optimized by density functional theory (DFT) using B3LYP/LANL2DZ. The calculated geometric parameters are in good agreement with the corresponding experimental values. Calculation results about these complexes show that dipole moment decreases, and the energy levels of HOMOs descend from iodo-complex to chloro-complex. The energy levels of HOMOs descend gently from iodo-complex to chloro-complex, while the energy levels of LUMOs in the present complexes are almost similar; therefore the energy gapes between HOMOs and LUMOs increased from iodo-complex to chloro-complex.

• Journal of the Korean Chemical Society
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• v.28 no.6
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• pp.384-392
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• 1984

Reaction of the Fe(II) complex of a fully saturated tetradentate macrocyclic ligand [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$, where [14]ane$N_4$ represents 1,4,8,11-tetraazacyclotetradecane, with $O_2$ has been investigated in acetonitrile solutions. [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$ reacts with oxygen to yield low spin Fe(III) species, [Fe([14]aneN$_4)(CH_3CN)_2]^{3+}$, which undergoes metal ion assisted oxidative dehydrogenation of the macrocyclic ligand to produce low spin Fe(II) complex, [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$. The macrocyclic ligand in [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$ is highly unsaturated and its double bonds are conjugated. [Fe([14]dieneN$_4)(CH_3CN)_2]^{2+}$ and [Fe([14]dieneN$_4)(CH_3CN)_2]^{3+}$ are isolated as the intermediates of the reaction. The Fe(II) complexes involved in this oxidative dehydrogenation reaction react with carbon monoxide to give respective carbon monoxide derivatives, [FeL$(CH_3CN)(CO)]^{2+}$ (where L = macrocyclic ligand). The values of $v_{CO}$ of [FeL$(CH_3CN)(CO)]^{2+}$, and the electrochemical oxidation potentials of Fe(II) ${\to}$ Fe(III) and the qualitative stability toward air-oxidation for [FeL(CH$_3CN_2)^{2+}$ increase as the degree of unsaturation of the macrocyclic ligands increase.

• Bulletin of the Korean Chemical Society
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• v.23 no.1
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• pp.81-85
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• 2002

A new di-N-cyanoethylated 14-membered tetraaza macrocycle 1,8-bis(2-cyanoethyl)-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane $(L^2)$ and its nickel(II) complex $[NiL^2(OAc)]^+$ have been prepared. The square-planar complex $[NiL^2](C IO_4)_2$ can be prepared by addition of $HClO_4$ to a hot aqueous solution of $[NiL^2(OAc)]^+$ The Ni-N (tertiary amino group) bond distances $(2.008{\AA})$ of $[NiL^2](C IO_4)_2$ are relatively long, and the complex exhibits a d-d transition band at unusually long wavelength (ca. 515 nm). The complex $[NiL^2](C IO_4)_2$ rapidly reacts with acetate ion or ethylenediamine (en) to produce $[NiL^2(OAc)]^+$ or [Ni(en)_3]^{2+}$, respectively, and is readily decomposed in NaOH (0.01 M) solution. The chemical properties of $[NiL^2]^{2+}$ as well as its synthetic procedure are quite different from those for other related 14-membered tetraaza macrocyclic complexes. Effects of the N-cyanoethyl and C-methyl groups on the properties of $L^2$.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.7 no.4
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• pp.733-737
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• 2006

In this paper, we report the coordination state and structure of $Zn(cyclam)Cl_{2})$ complex that was studied by the Raman spectrum and conductivity method. The complex of zinc(II) ion with 1,4,8,11-tetraazacyclotetradecane(cyclam) ligand is formed in aqueous solution. According to the Raman spectrum of $Zn(cyclam)Cl_{2})$ complex, $H_{2}O$ molecule and $Cl^{-}$ ion compete for the trans coordination site of zinc(II) ion. We also have investigated the competition effect of $H_{2}O$ molecule and $Cl^{-}$ ion by the conductivity method. On addition of 1,4,8,11-tetraazacyclotetradecane(cyclam) ligand to the aqueous $ZnCl_{2}$ solution, 2: 1 electrolyte is changed to 1:1 electrolyte. We suggest the possibility of elimination of heavy metal because of the affinity effect of macrocyclic polyamine(1,4,8.11-tetraazacyclotetradecane) for the heavy metal,.

• Bulletin of the Korean Chemical Society
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• v.31 no.7
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• pp.2069-2072
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• 2010

• Bulletin of the Korean Chemical Society
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• v.31 no.1
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• pp.189-192
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• 2010

• Bulletin of the Korean Chemical Society
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• v.24 no.3
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• pp.393-396
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• 2003

• Bulletin of the Korean Chemical Society
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• v.25 no.12
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• pp.1757-1763
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• 2004

A new series of nickel(II), cobalt(II)/(III) and copper(II) complexes of 14, 15 and 16-membered of macrocyclic ligands have been prepared and characterized by elemental analyses, IR, UV-VIS and $^1H-NMR$ spectra, magnetic susceptibilities, conductivities, DTA and ESR measurements. Molar conductances in DMF solution indicate that, the complexes are nonelectrolytes except (9-12) complexes. The electronic spectra show that, all complexes are square planar or distorted octahedral geometry. The ESR spectra of solid complexes (4), (8) and (11) show square planar of axial type symmetry $(d_{x2-y2})$ with considerable covalent bond character. However, complex (12) shows a spectrum of octahedral geometry with $d_{z2}$ ground state. Complex (12) shows exploitation in reducing the amount of electron adducts formed in DNA during irradiation with low radiation products.

• Journal of the Korean Electrochemical Society
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• v.10 no.3
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• pp.190-195
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• 2007

A new electrochemical sensor to selectively determine epinephrine was developed and its analytical characteristics has been investigated. A glassy carbon electrode was modified with Ni(II)-macrocyclic complex which has electrocatalytic effect. It was further modified with physiologically suitable and negatively charged polyuretane benzyl L-glutamate(PUBLG). The present electrode showed long term stability and it could be applied to the selective determination of epinephrine in urine sample with various coexisting compounds. Under the optimum experimental conditions the linear range was $8.0\;{\times}\;10^{-7}\;-\;2.0\;{\times}\;10^{-4}\;M$ and the limit of detection was $1.0\;{\times}\;10^{-7}\;M$. The recovery of epinephrine in urine sample diluted 5 times with buffer solution was $101.5({\pm}3.2)%$ for 6 measurements.

• Bulletin of the Korean Chemical Society
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• v.9 no.5
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• pp.292-295
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• 1988

Macrocyclic ligands have been studies as cation carriers in a bulk liquid membrane system. $Cu^{2+}$ has been transported using nitrogen substituted macrocycles as carriers and several transition metal ions($M^{n+}\;=\;Mn^{2+},\;Co^{2+},\;Ni^{2+},\;Cd^{2+},\;Pb^{2+}\;and\;Ag^{+}$) have been transported using $DBN_3O_2,\;DBN_2O_2,\;Me_6N_414C4$ and DA18C6 as carriers in a bulk liquid membrane system. Competitive $Cu^{2+}-M2^+$ transport studies have also been carried out for the same system. In single cation transport experiments, the best macrocyclic ligand for transport is a ligand that gives a moderately stable rather than very stable complex in the extraction. However, when both cations are present in the source phase, the cation which forms the most stable complex with carrier is favored in transport over other cations. Generally, the nitrogen substiituted macrocycles transport $Cu^{2+}$ selectively over $Mn^+$. Ligand structure, equilibrium constant (or stability constant) for complex formation, source phase pH and carrier concentration are also important parameters in transport experiments.