• Bulletin of the Korean Chemical Society
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• v.12 no.2
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• pp.219-224
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• 1991

New binuclear Ni(Ⅱ) and Cu(Ⅱ) complexes with various alkyl derivatives of 1,2-bis(1,3,6,8,10,13-hexaaza-1-cyclotetradecyl) ethane, in which two fully saturated 14-membered hexaaza macrocyclic subunits are linked together by an ethylene chain, have been synthesized by the one step template condensations of formaldehyde with ethylenediamine and appropriate primary alkyl amines in the presence of the metal ions. Each macrocyclic subunit of the double-ring macrocyclic complexes contains one alkyl pendant arm and has a square planar geometry with a 5-6-5-6 chelate ring sequence. The visible spectra and oxidation properties indicate that the metal-metal interaction of the binuclear complexes are not significant. Synthesis, characterization, and the properties of the complexes are presented.

• Bulletin of the Korean Chemical Society
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• v.17 no.4
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• pp.331-334
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• 1996

New copper(Ⅱ) complex of the pentaaza non-macrocyclic ligand 1-(2-aminoethyl)-3-(N-{2-aminoethyl}aminomethyl)-1,3-diazacyclohexane (2) and a dinuclear copper(Ⅱ) compex of the bis(macrocyclic) ligand 3, in which two 1,5,8,10,12,15-hexaazabicyclo[11.3.11.5]heptadecane subunits are linked together by an ethylene chain through the uncoordinated nitrogen (N10) atoms, have been prepared selectively by the reaction of the metal ion, 1,4,8-triazaoctane, ethylenediamine, and formaldehyde. The dinuclear complex [Cu2(3)]4+ has been also prepared by the reaction of [Cu(2)]2+ with ethylenediamine and formaldehyde. The reaction products largely depend on the molar ratio of the reactants employed. The mononuclear complex or each macrocyclic subunit of the dinuclear complex contains one 1,3-diazacyclohexane ring and has a square-planar geometry with a 5-6-5 or 5-6-5-6 chelate ring sequence. In acidic solution, the copper(Ⅱ) complex of 2 dissociates more slowly than those of other related non-cyclic polyamines.

• Bulletin of the Korean Chemical Society
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• v.16 no.7
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• pp.649-653
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• 1995

Solution-state structure of native F430 was determined by using NMR methods and NMR-based distance geometry (DG) computations. Structures were generated with loose NOE-derived interproton distance restraints (2.0-2.5 Å, 2.0-3.5 Å and 2.0-4.5 Å for strong, medium, and weak NOE cross-peak intensities, respectively). 2D NOESY back-calculations of structures were subsequently carried out for establishing the consistence between experimental data and DG-model structures. The back-calculated 2D NOESY spectra of resulting DG structures were well consistent with experimental 2D NOESY spectra. Superposition of 20 independent structures with macrocyclic ring atoms and all atoms of F430 afforded pairwise root mean square deviations (RMSD) of 0.025-0.125 Å and 0.64-1.3 Å, respectively. The macrocyclic rings of structures are well converged to a unique conformation with saddle-shaped deformation whereas most of side chains are not converged. The average dihedral angle (N1-N2-N3-N4, 27.78±1.50°) of 20 DG-structures exhibits that the macrocyclic ring conformation is puckered as much as 12,13-diepimeric F430 (28.75±4.07°).

• 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.23 no.5
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• pp.708-714
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• 2002

The hexanuclear metallamacrocycles were observed repeatedly in various conditions including the presence of several different tricationic metal ions in the macrocyclic ring system and of the linear alkyl chains at the acyl site of N-acylsalicylhydrazide ligand, which contrasts to the formation of the decanuclear metallamacrocycle with bulkier side chains such as phenyl group at the acyl site of the ligand. We synthesized a series of metallamacrocycles in various solvents to find the relationship between the solvents and the nuclearity of the metallamacrocycles. Whether the solvents are sterically more demanding or not, the complexes formed kept the hexanuclear metallamacrocycle system.

• Bulletin of the Korean Chemical Society
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• v.23 no.11
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• pp.1629-1634
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• 2002

Reaction of tetrahomodioxa p-phenylcalix[4]arene with alkyl halide and NaH in DMF leads to the title tetra-alkylated derivatives, 7,13,21,27-tetra-phenyl-29,30,31,32-tetraalkyloxy-2,3,16,17-tetrahomo-3,17-dioxacalix [4]arenes, their preferred conformations were determined by NMR spectra as C-1,2-alternate. The molecular structure of allyl derivative has been solved by X-ray diffraction methods. The molecules have a conformation with pseudo center of symmetry. The benzene ring A is up, ring C is down, B and D rings are flat with respect to the plane of the macrocyclic ring.

• Bulletin of the Korean Chemical Society
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• v.17 no.12
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• pp.1112-1117
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• 1996

The electronic structures of twenty-seven isomers of a macrocyclic fulleropyrrolidine are investigated with semi-empirical extended Huckel (EH) molecular orbital method. The geometry of each isomer is determined by the molecular mechanics and dynamics methods based on UFF (universal force field) empirical force field. The calculated geometries, such as the carbon-carbon distances of the fullerene moiety, are in good agreement with those of related fullerene derivatives. The EH calculation shows that the formation of macrocyclic pyrrolidine ring on fullerene moiety results in the reduction of the HOMO-LUMO energy gap. From the graphical analysis of the DOS (density of states), PDOS (projected DOS), and MOOP (molecular orbital overlap population) curves, we can find that this reduction is due to splitting of the HOMO of fullerene moiety, which results from the symmetry-breaking and the distortion of the buckminsterfullerene framework from its ideal icosahedral structure.

• Journal of the Korean Magnetic Resonance Society
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• v.3 no.1
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• pp.44-51
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• 1999

An enzyme derived conformational changes of cobalamine is thought to be important in the homolytic cleavage of Co-C bond which is the first step of catalytic Cl-cycle of coenzyme B12-dependent enzymes. Modern 2D-NMR and NMR-based distance geometric studies were carried out to determine the 3D structure of corrin ring. Homonuclear and heteronuclear correlation NMR experiments were performed for complete 1H-NMR signal assignments. Distances between numerous proton pairs were deduced based on the NOE cross peak intensities and subsequently used as input into the distance geometry program for the 3D structure determination. The detailed 3D structure from the present NMR-based analysis was compared with the result from X-ray crystallographic study, which revealed greater conformational changes occur in benzimidazole group and sugar ring than in macrocyclic corrin and tetrapyrrole. In addition, the distance geometry used in this study was found to be quite useful for NMR-based structure determination of medium-sized molecules that give poor NOE effects arising from their intermediate tumbling rate ($\omega$$\tau$c 1.0).

• Journal of the Korean Magnetic Resonance Society
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• v.21 no.4
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• pp.139-144
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• 2017

Ni(II) containing coenzyme F430 catalyzes the reduction of $CO_2$ in methanogen. Macrocyclic Ni(II) complexes with N,O shiff bases have been received a great attention since metal ions play an important role in the catalysis of reduction. The reducing power of metal complexes are supposed to be dependent on oxidoreduction state of metal ion and structural properties of macrocyclic ring moiety that can enhance electrochemical properties in catalytic process. Six different ${\alpha}$-oximinoketone compounds, precursor of macrocyclic ligands used in $CO_2$ reduction coenzyme F430 model complexes, were synthesized with yields over 90% and characterized by NMR. The molecular geometries of ${\alpha}$-oximinoketone analogues were fully optimized at Beck's-three-parameter hybrid (B3LYP) method in density functional theory (DFT) method with $6-31+G^*$ basis set using the ab initio program. In order to understand molecular planarity and substitutional effects that may enhance reducing power of metal ion are studied by computing the structure-dependent $^{13}C$-NMR chemical shift and comparing with experimental results.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.320-320
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• 2006

The authors report the synthesis and radical ring-crossover polymerization of macrocycles with radically exchangeable dynamic covalent bonds. The macrocyclic compounds with alkoxyamine units were designed and synthesized by condensation from alkoxyamine-based diol and the corresponding acid chlorides in the presence of pyridine under high-dilution condition. The macrocycles can thermally polymerize by intermolecular radical crossover reaction. Furthermore, the poly(alkoxyamine)s depolymerized to the monomers principally by the intramolecular radical exchange process under high-dilution conditions.