• Bulletin of the Korean Chemical Society
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• v.17 no.9
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• pp.790-793
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• 1996

The azacrown compound, 1,7-dioxa-4,10,13-triazacyclopentadecane-N,N',N"-tri(methyl-acetic acid)(N3O2-tri(methylacetic acid)) was synthesized by modified procedure of Krespan. Potentiometric method has been used to determine the protonation constants of N3O2-tri(methylacetic acid) and stability constants of complexes on the divalent transition metal ions (Co2+, Ni2+, Cu2+, and Zn2+) and trivalent metal ions (Ce3+, Eu3+, Gd3+, and Yb3+) with N3O2-tri(methylacetic acid). The stability constants for the complexes of the divalent transition metal ions studied in the present work with N3O2-tri(methylacetic acid) were 11.4 for Co2+, 11.63 for Ni2+, 13.51 for Cu2+, and 11.65 for Zn2+, respectively. Thus, the order of the stability constants for complexes on the transition metal ions with N3O2-tri(methylacetic acid) was shown Co2+ < Ni2+ < Cu2+ > Zn2+ as same as the order of Irving-Williams series. The stability constants of Ce3+, Eu3+, Gd3+, and Yb3+ trivalent lanthanide metal ion complexes of N3O2-tri(methylacetic acid) were, respectively, 11.26 for Ce3+, 11.56 for Eu3+, 11.49 for Gd3+, and 11.80 for Yb3+. The values of the stability constants on trivalent metal ions with the ligand are increasing according to increase atomic number, due to increase acidity. But the value of stability constant of Gd3+ ion is less than the value of Eu3+ ion. This disordered behavior is also reported by Moeller.

• Journal of the Korean Chemical Society
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• v.62 no.1
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• pp.14-18
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• 2018

The complexes $[Zn(L)(H_2O)_2]{\cdot}2NO_2$ (1) and $[Zn(L)(NO_3)_2]$ (2) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo $[14,4,0^{1.18},0^{7.12}]$docosane) have been synthesized and structurally characterized. The compound 1 crystallizes in the monoclinic system $P2_1/c$ with a = 8.74650(10), b = 18.6880(3), c = $7.96680(10){\AA}$, ${\beta}=109.1920(10)^{\circ}$, $V=1229.84(3){\AA}^3$, Z = 2. The compound 2 crystallizes in the monoclinic system P1 with a = 8.1292(5), b = 8.9244(5), c = $9.1398(5){\AA}$, ${\alpha}=68.035(2)$, ${\beta}=70.109(2)$, ${\gamma}=75.649(3)^{\circ}$, $V=572.70(6){\AA}^3$, Z = 1. The crystal structures of the compounds 1 and 2 show a distorted octahedral coordination geometry around the zinc(II) ion, with four secondary amines and two oxygen atoms of the two water and two nitrate ligands at the axial position. The TGA behaviors of the complexes are significantly affected by the nature of the tetraaza macrocycle and the axial ligands.

• Bulletin of the Korean Chemical Society
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• v.24 no.3
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• pp.269-273
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• 2003

The synthesis and properties of 2,13-bis(3'-pyridylmethyl) $(L^3)$, 2,13-bis(4'-pyridylmethyl) $(L^4)$, and 2,13-bis(phenylmethyl) $(L^5)$ derivatives of 5,16-dimethyl-2,6,13,17-tetraazatrcyclo$[16.4.0.^{1.18}0^{7.12}]$docosane are reported. The 3- or 4-pyridylmethyl groups of $[ML^3](ClO_4)_2\;or\;[ML^4](ClO_4)_2$ (M = Ni(Ⅱ) or Cu(Ⅱ)) are not involved in coordination, and the coordination geometry (square-planar) and ligand field strength of the complexes are quite similar to those of $[ML^5](ClO_4)_2$, bearing two phenylmethyl pendant arms. However, the complex formation reactions of $L^3\;and\;L^4$ are strongly influenced by the pyridyl groups, which can interact with a proton or metal ion outside the macrocyclic ring. The macrocycle $L^5$ exhibits a high copper(Ⅱ) ion selectivity against nickel(Ⅱ) ion; the ligand readily reacts with copper(Ⅱ) ion to form $[CuL^5]^{2+}$ but does not react with hydrated nickel(Ⅱ) ion in methanol solutions. On the other hand, $L^3\;and\;L^4$ form their copper(Ⅱ) and nickel(Ⅱ) complexes under a similar condition, without showing any considerable metal ion selectivity. The ligands $L^3\;and\;L^4$ react with copper(Ⅱ) ion more rapidly than does $L^5$ at pH 6.4. At pH 5.0, however, the reaction rate of the former macrocycles is slower than that of the latter. The effects of the 3- or 4-pyridylmethyl pendant arms on the complex formation reaction of $L^3\;and\;L^4$ are discussed.

• Journal of the Korean Chemical Society
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• v.33 no.6
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• pp.588-595
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• 1989

Log K, ${\Delta}$H and ${\Delta}$S for the complexation of $La^{3+},\;Ce^{3+}$ and $Eu^{3+}$with various multidentate ligand containing crown ether, diaza crown ether and diamine ether have been determined in methanol and acetonitril solutions at $25^{\circ}C$ by solution calorimetric titration method. The greater stability constant of $La^{3+}$-15C5 than those of 18C6 diaza [2.2] in methanol are discussed in terms of the size of metal ion and the ligand cavity and of metal ion solvation. The stabilities of $Ce^{3+}$ and $La^{3+}$ ion complexes with a various multidentate ligand in acetonitril are in the order of (diamine ether)<18C6<15C5$Ce^{3+}$, $La^{3+}$ and $Eu^{3+}$-diaza [2.2] complexes in acetonitril are increased with the following order: $Eu^{3+}$ < $La^{3+}$ < $Ce^{3+}$, that is increasing order of the optimum size and of the charge density of metal ion.

• Analytical Science and Technology
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• v.8 no.4
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• pp.449-456
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• 1995

Novel macrocyclic ligands modified with pendant arms, N, N', N'', N''', N'''', N'''''-hexakis(2-aminoethyl)-1, 4, 7, 10, 13, 16-hexaazacyclootadecane [$L_3$, Fig.1] and 1, 4, 7-tris(3-(o-hydroxyphenyl)propyl)-1, 4, 7-triazacyclononane [$L_4$, Fig.1] have been synthesized, and the protonation of $L_3$ and $L_4$ and stability constants of $L_3$ with bivalent transition metal ions and rare earth metal ions were determined by a potentiometry. The obtained results show that the complex formation of $L_3$ depends on the metal ligand ratios, and the stability of the metal complexes does not depend on the sizes of the metal ions, but on the nature of the metal ions. The structures of the rare earth complexes for $L_4$ were characterized by an X-ray absorption spectrometry(XAFS).

• Journal of the Korean Chemical Society
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• v.31 no.6
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• pp.503-508
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• 1987

The protonation constants of 3,4 : 9,10-dibenzo-1,12-diaza-5,8-dioxacyclotetradecane $(NenOenH_4)$ and stability constants of its transition metal complexes have been determined by the potentiometric titration in 1 : 1 dioxane-water mixture with 0.1 ionic strength at $25^{\circ}C.$ For a given anion system, the stabilitv constants of the complexes are in the order of $Mn^{2+}<\;Co^{2+}\;< Ni^{2+}\;<\;Cu^{2+}\;>\;Zn^{2+}$, which accords with the Williams-Irving series.

• Proceedings of the Korean Fiber Society Conference
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• 2002.04a
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• pp.195-198
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• 2002

Poly(crown ether)s as a functional polymer materials have powerful and selective complexation properties with a large number of metal cations and have advantage of facility of their recovery and modification of their complexation properties in contrast to their monomeric analogues. Poly(crown ether)s having pendant macrocyclic groups can easily form 2:1-type crown ether ring-to-cation complexes with particular metal ions which are a little larger than the cavity of the crown ether ring. (omitted)

• Bulletin of the Korean Chemical Society
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• v.17 no.9
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• pp.814-819
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• 1996

In search of simple host molecules for uranyl ion which form 1: 1-type complexes with high formation constants that can be used either in extraction of uranium from seawater or in catalysis of biologically important organic reactions, the uranophile activities of dihydroxyazobenzene derivative 1 were studied. Uranyl ion and 1 form a 1: 1-type complex with a very large formation constant. The formation constant was measured at pH 7-11.6 by competition experiments with carbonate ion. From the resulting pH dependence, ionization constants of the two aquo ligands coordinated to the uranium of the uranyl complex of 1 were calculated. The ionization constants were also measured by potentiometric titration of the uranyl complex of 1. Based on these results, the pKa values of the two aquo ligands were estimated as 7.1 and 11.0, respectively. At pH 7.5-9.5, therefore, the complex exists mostly as monohydroxo species. Under the conditions of seawater, 1 possesses greater affinity toward uranyl ion compared with other uranophiles such as carbonate ion, calixarene derivatives, or a macrocyclic octacarboxylate. In addition, complexation of 1 with uranyl ion is much faster than that of the calixarene or octacarboxylate uranophiles.

• Bulletin of the Korean Chemical Society
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• v.25 no.2
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• pp.216-220
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• 2004

${\beta}$-CD and CM- ${\beta}$-CD as chiral NMR shift agents were used to resolve the enantiomers of noradrenaline (NA). The stoichiometry of each complex formed between the CDs and the enantiomers of NA was found to be 1 : 1 through the continuous variation plots. The binding constants (K) of the complexes were determined from $^1H$ NMR titration curves. This result indicated that both ${\beta}$-CD and CM- ${\beta}$-CD formed the complexes with the S(+)-NA more preferentially than its R(-)-enantiomer. The K values for the complexes with ${\beta}$-CD ($K_{S(+)}$ = 537 $M^{-1}$ and $K_{R(-)}$ = 516 $M^{-1}$ was larger than those with CM- ${\beta}$-CD ($K_{S(+)}$ = 435 $M^{-1}$ and $K_{R(-)}$ = 313 $M^{-1}$), however, enantioselectivity (${\alpha}$) of S(+)- and R(-)-NA to CM- ${\beta}$-CD ( ${\alpha}$ = 1.38) was larger than that to ${\beta}$-CD ( ${\alpha}$ = 1.04), indicating that CM- ${\beta}$-CD was the better chiral NMR solvating agents for the recognition of the enantiomers of NA. Two dimensional rotating frame nuclear Overhauser enhancement spectroscopy (ROESY) experiments were also performed to explain the binding properties in terms of spatial fitting of the NA molecule into the macrocyclic cavities.

• Membrane Journal
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• v.24 no.6
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• pp.472-483
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• 2014

This study is preparation of microporous membranes by using macrocyclic metal ion complexes and extended cage complexes. It is a more favorable way to existing methods because polymer and metal ion-ligand complex system provides a fine control over the phase transition behavior. Chemical functionalization of the polar surface can be obtained. Metal-templated condensation of cyclohexanedione dioxime, hydroxyphenylboronic acid in the presence of metal salts proceeds cleanly in methanol to furnish the metal clathrochelate complexes. Organic/inorganic hybrid membranes were prepared with polyethersulfone (PES), polyvinylpyrrolidone (PVP), ethyleneglycol butyl ether (BE), metal clathrochelate s and DMF by using nonsolvent induced phase inversion method. The structure of membranes was characterized with scanning electron microscopy (SEM) and microflow permporometer. The addition of Fe(II) clathrochelate complex with p-hydroxyphenyl group leads to changes of membrane morphology such as narrow mean pore size distribution, increase of surface pore density and decrease of the largest pore size.