• Bulletin of the Korean Chemical Society
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• v.33 no.12
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• pp.4231-4234
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• 2012

• Bulletin of the Korean Chemical Society
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• v.29 no.6
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• pp.1273-1276
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• 2008

• Bulletin of the Korean Chemical Society
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• v.16 no.6
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• pp.518-523
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• 1995

New square planar nickel(Ⅱ) complexes with various 1-alkyl (4a-4c) and 1-hydroxyalkyl (4d-4f) derivatives of the 14-membered pentaaza macrocycle 8-ethyl-8-nitro-1,3,6,10,13-pentaazacyclotetradecane have been synthesized by two-step metal template condensation reactions of ethylenediamine, nitroethane, formaldehyde, and appropriate primary amines. The nitro group and/or hydroxyl group of 4a-4f are not directly involved in the coordination. The nickel(Ⅱ) complexes exist in coordinating solvents such as MeCN, Me2SO, and H2O as equilibrium mixtures of the square planar [Ni(L)]2+(L=4a-4f) and octahedral species [Ni(L)S2]2+(S=solvent molecule). Although the ligand field strength and redox potentials of the complexes are not affected by the nature of the substituents, the formation of octahedral species for 4d-4f in MeCN is strongly restricted by the hydroxyl group. Synthesis, characterization, and solution behaviors of the nickel(Ⅱ) complexes are described.

• Bulletin of the Korean Chemical Society
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• v.10 no.4
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• pp.362-366
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• 1989

Square planar nickel(II) and copper(II) complexes of 14-membered macrocyclic ligands containing various alkyl pendant arms at the uncoordinated nitrogen atoms, 1,8-dipropyl, 1,8-dibutyl, 1,8-bis(2-methylpropyl), 1,8-bis(2-ethylhexyl), and 1,8-dibenzyl-1,3,6,8,10,13-hexaazacyclotetradecane have been prepared from the template condensation of ethylenediamine, formaldehyde, and appropriate primary amines in the presence of the metal ion. The spectroscopic and electrochemical properties of these complexes are similar to those of tetraaza macrocyclic complexes and are not affected significantly by the nature of the alkyl groups.

• Journal of Environmental Science International
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• v.16 no.6
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• pp.689-698
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• 2007

Mesoporous silicas for heavy metals adsorption were prepared by co-condensation of surfactant as a template and Ludox HS-40 as a silica precursor. Various mesoporous silicas with the introduction of chelating ligands (mercaptopropyl and aminopropyl groups) were synthesized to remove heavy metal ions from aqueous solutions. The surface modification was conducted with a co-condensation process using the sequential or simultaneous addition of mesoporous silica and high concentration of the organosilane(3-mercaptopropyltrimethoxysilane and 3-aminopropyltriethoxysilane). These materials have been characterized by elemental analysis, XRD, SEM and TEM analysis. Adsorbents synthesized with 3-mercaptopropyltrimethoxysilane and 3-aminopropyltriethoxysilane shows a high loading capacity for Hg(II), Pb(II), Cd(II) and anion Cr(VI). Especially the one synthesized with a mercaptopropyl function has the highest adsorption capacity for Hg(II) and Cd(II).

• Bulletin of the Korean Chemical Society
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• v.32 no.3
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• pp.1037-1040
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• 2011

The dinuclear complex 1 with cooperative hydrogen bonds can be prepared by the metal-directed reaction of Eq. (2). This work shows that the coordinated hydroxyl group trans to the secondary amino group is deprotonated more readily than that trans to the tertiary amino group and acts as the hydrogen-bond accepter. The lattice water molecules in 1 act as bridges between the two mononuclear units through hydrogen bonds. The complex is quite stable as the dimeric form even in various polar solvents. The complex exhibits a weak antiferromagnetic interaction between the metal ions in spite of relatively long Cu$\cdots$Cu distance. This strongly supports the suggestion that the antiferromagnetic behavior is closely related to the cooperative hydrogen bonds.

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2125-2130
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• 2013

A new nickel(II) complex $[NiL^1]^{2+}$ ($L^1$ = 1-(2-aminoethyl)-3-(N-{2-aminoethyl}aminomethyl-1,3-diazacyclohexane) containing one 1,3-diazacyclohexane ring has been prepared selectively by the metal-template condensation of formaldehyde with N-(2-aminoethyl)-1,3-propanediamine and ethylenediamine at room temperature. The complex reacts with nitroethane and formaldehyde to yield the pentaaza macrocyclic complex $[NiL^2]^{2+}$ ($L^2$ = 8-methyl-8-nitro-1,3,6,10,13-pentaazabicyclo[13.3.1]heptadecane) bearing one C-$NO_2$ pendant arm. The reduction of $[NiL^2]^{2+}$ by using Zn/HCl produces $[NiL^3(H_2O)]^{2+}$ ($L^3$ = 8-amino-8-methyl-1,3,6,10,13-pentaazabicyclo[13.3.1]heptadecane) bearing one coordinated C-$NH_2$ pendant arm that is readily protonated in acid solutions. The hexaaza macrocyclic complex $[NiL^4]^{2+}$ ($L^4$ = 8-phenylmethyl-8-nitro-1,3,6,8,10,13-hexaazabicyclo[13.3.1]heptadecane) bearing one N-$CH_2C_6H_5$ pendant arm has also been prepared by the reaction of $[NiL^1]^{2+}$ with benzylamine and formaldehyde. The nickel(II) complexes of $L^1$, $L^2$, and $L^4$ have square-planar coordination geometry in the solid states and in nitromethane. However, they exist as equilibrium mixtures of the square-planar $[NiL]^{2+}$ (L = $L^1$, $L^2$, or $L^4$) and octahedral $[NiL(S)_2]^{2+}$ species in various coordinating solvents (S); the proportion of the octahedral species $[NiL(S)_2]^{2+}$ is strongly influenced by the ligand structure and the nature of the solvent. Synthesis, spectra, and chemical properties of the nickel(II) complexes of $L^1-L^4$ are described.

• Bulletin of the Korean Chemical Society
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• v.15 no.5
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• pp.374-378
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• 1994

Square planar nickel(II) complexes with various 1-alkyl derivatives of the 14-membered pentaaza macrocycle 8-methyl-8-nitro-1,3,6,10,13-pentaazacyclotetradecane can be readily prepared by two-step metal template condensation reactions of ethylenediamine, nitroethane, formaldehyde, and appropriate primary alkylamines. In coordinating solvents the nickel (II) complexes form octahedral species containing two axially coordinated solvent molecules and thus show square planar-octahedral equilibrium. The properties of the pentaaza macrocyclic complexes are considerably different from those of the complexes of analogous hexaaza and tetraaza macrocyclic complexes. Synthesis, characterization, and spectroscopic and chemical properties of the new complexes are described.

• Bulletin of the Korean Chemical Society
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• v.14 no.2
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• pp.292-294
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• 1993

Three derivatives of poly(ethylenimine) (PEI) are prepared by Ni(II)-template condensation with glyoxal(GO): PEI[Ni(II)-GO]$_{0.08}$ (1), PEI[Ni(II)-GO]$_{0.03}$ (2), and lau$_{0.18}$PEI[Ni(II)-GO]$_{0.03}$ (3). The contents of Ni(II)-macrocyclic center of 1-3 are 8%, 3%, or 3%, respectively, of the monomer residues, and 18% of monomer residues for 3 are laurylated. The pH profiles for k$_{cal}$ and k$_m$ for the deacylation of 4-carboxy-2-nitrophenyl acetate are measured. The relative magnitude of the parameters for 1-3 and different shapes of the pH profiles for 1-3 are explained in terms of the electrostatic and the hydrophobic effects exerted by the metal centers and lauryl groups. For the artificial metalloenzymes built on PEI, therefore, the ionization of functional groups and the affinity toward counter-anions can be controlled by adjusting charge density and the content of hydrophobic groups.

• Journal of the Korean Chemical Society
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• v.33 no.5
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• pp.510-515
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• 1989

New nickel(II) and coppr(II) complexes of a saturated pentaaza macrobicyclic ligand $[Ni(D)]^{2+},\;[Cu(D)]^{2+},\;and\;[Cu(D)Cl]^+$, where D is 1,3,6,9,12-pentaazabicyclo[10,2,l]pentadecane, have been prepared by the template condensation reaction of tetraethylenepentamine and formaldehyde in the presence of the metal ion. The complexes contain one imidazolidine ring in the macrobicyclic ligand, D. The complexes $[Ni(D)]^{2+}\;and\;[Cu(D)]^{2+}$ have square planar geometry with 5-5-5-6 chelate ring sequence. The electronic spectra of $[Cu(D)Cl]^+$indicate that the complex has square pyramidal geometry. Synthesis, charactrization, and the spectroscopic and chemical properties of the macrobicyclic nickel(II) and copper(II) complexes are described.