• Bulletin of the Korean Chemical Society
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• v.35 no.1
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• pp.269-272
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• 2014

• Bulletin of the Korean Chemical Society
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• v.30 no.12
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• pp.3101-3104
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• 2009

• Journal of the Korean Chemical Society
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• v.63 no.3
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• pp.209-212
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• 2019

• Bulletin of the Korean Chemical Society
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• v.34 no.1
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• pp.255-258
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• 2013

• Bulletin of the Korean Chemical Society
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• v.33 no.8
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• pp.2517-2522
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• 2012

New polynuclear poly(hexaaza macrocyclic) copper(II) complexes $[1](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$, $[2](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$, and $[3](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$ have been prepared by the one-pot reaction of formaldehyde with ethylenediamine and 1,2-bis(2-aminoethoxy)ethane, 1,3-diaminopropane, or 1,6-diaminohexane in the presence of the metal ion. The polymer complexes contain fully saturated 14-membered hexaaza macrocyclic units (1,3,6,8,10,13-hexaazacyclotetradecane) that are linked by $N-(CH_2)_2-O-(CH_2)_2-O-(CH_2)_2-N$, $N-(CH_2)_3-N$, or $N-(CH_2)_6-N$ chains. The mononuclear complex $[Cu(H_2L^5)](ClO_4)_4$ ($H_2L^5$ = a protonated form of $L^5$) bearing two $N-(CH_2)_2-O-(CH_2)_2-O-(CH_2)_2-NH_2$ pendant arms has also been prepared by the metal-directed reaction of ethylenediamine, 1,2-bis(2-aminoethoxy)ethane, and formaldehyde. The polymer complexes were characterized employing elemental analyses, FT-IR and electronic absorption spectra, molar conductance, X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and scanning electron micrograph (SEM). Electronic absorption spectra of the complexes show that each macrocyclic unit of them has square-planar coordination geometry with a 5-6-5-6 chelate ring sequence. The polymer complexes as well as $[Cu(H_2L^5)]^{4+}$ are quite stable even in concentrated $HClO_4$ solutions. Synthesis and characterization of the polynuclear and mononuclear copper(II) complexes are reported.

• 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.

• Bulletin of the Korean Chemical Society
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• v.33 no.7
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• pp.2381-2384
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• 2012

• Bulletin of the Korean Chemical Society
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• v.10 no.6
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• pp.605-606
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• 1989

• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2565-2570
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• 2011

The reaction of bromoacetonitrile with 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[$16.4.1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^{10}$) containing a N-$CH_2$-N linkage produces 17-cyanomethyl-3,14-dimethyl-2,6,13,17-tetraazatetracyclo-[$16.4.1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^{11}$). The mono-N-functionalized macrocyclic complexes $[ML^2]^{2+}$ (M = Ni(II) or Cu(II); $L^2$ = 2-cyanomethyl-5,16-dimethyl-2,6,13,17-tetraazatricyclo[$16.4.0.0^{7.12}$]docosane) can be prepared by the reaction of $L^{11}$ with nickel(II) or copper(II) ion in acetonitrile. The N-$CH_2CN$ group attached to $[ML^2]^{2+}$ readily reacts with water or methanol to yield the corresponding complexes of $HL^3$ bearing one N-$CH_2CONH_2$ pendant arm or $L^4$ bearing one $N-CH_2C(=NH)OCH_3$ group. The $N-CH_2CONH_2$ or $N-CH_2C(=NH)OCH_3$ group of each complex is coordinated to the central metal ion. Both $[NiL^4(H_2O)]^{2+}$ and $[CuL^4]^{2+}$ are quite stable in acidic aqueous solutions, but undergo hydrolysis to yield $[Ni(HL^3)(H_2O)]^{2+}$ or $[Cu(HL^3)]^{2+}$ in basic aqueous solutions. In contrast to $[Cu(HL^3)]^{2+}$, $[Ni(HL^3) (H_2O)]^{2+}$ is readily deprotonated to form $[NiL^3 (H_2O)]^+$ ($L^3$ = a deprotonated form of $HL^3$) in basic aqueous solutions.

• Bulletin of the Korean Chemical Society
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• v.21 no.11
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• pp.1106-1110
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• 2000

New 14-membered tetraaza macrocycles 1,8-diallyl-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane $(L^2)$ and 1,8-bis(n-propyl)-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane $(L^3)$ have been prepared by direct react ion of 2,5,5,7,9,12,12,14-octamethyl-1,4,8,11-tetraazacyclotetradecane $(L^1)with$ allyl bromide or n-propyl bromide. The nickel(II) and copper(II) complexes of $L^2andL^3have$ been prepared. The macrocycles show high copper(II) selectivity against nickel(II) ion in methanol solutions containing water. The wavelengths (ca. 505 nm) of the d-d bands for the nickel(II) complexes are extraordinarily longer than those for the complexes of $L^1and$ other related di-N-alkylated 14-membered tetraaza macrocycles. Crystal structure of $[NiL^2](ClO4)_2$ shows that the average Ni-N bond distance $(1.992\AA)$ of the complex is distinctly longer than those of other related nickel(II) complexes. Effects of the N- and C-substituents on the properties of the macrocyclic compounds are discussed.