• Bulletin of the Korean Chemical Society
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• v.24 no.8
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• pp.1150-1154
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• 2003

The reactions of [Ni(L)(H₂O)₂]Cl₂ (L = 2,5,9,12-tetramethyl-1,4,8,11-tetraazacyclotetradecane) with terephtalate (tp) and 2,5-pyridinedicarboxylate (pdc) generate one-dimensional nickel(II) complexes, [Ni(L)(H₂O)₂](tp) · ₄H₂O (1) and [Ni(L)(H₂O)₂](pdc)·₄H₂O (2). The structures have been characterized by X-ray crystallography, magnetic susceptibility and spectroscopy. The crystal structures of 1 and 2 show a distorted octahedral coordination geometry around the Ni(II) ion, with secondary amines of the macrocycle and two water molecules at the trans position. Complexes 1 and 2 display the one-dimensional hydrogen-bonded infinite chains. The magnetic behavior of all compounds exhibits weak interchain antiferromagnetic interactions with J values of -1.09(3) for 1 and -1.14(2) cm-1 for 2.

• Journal of the Korean Chemical Society
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• v.31 no.5
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• pp.434-443
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• 1987

The formation constants of the complexes between Ln-EDTA 1 : 1 complex and IMDA have been investigated by a potentiometric titration method at 20.0${\pm}$0.2 degree C and ${\mu}$ = 0.1 (KNO$_3$). Unusually large stability in Ln(EDTA) mixed ligand complexes was found. Trends in the formation constants vs. atomic number of the lanthanide metals were discussed on the basis of coordination number and ionic radius of the metals.

• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.2041-2044
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• 2007

The reactions of mercury(II) chloride with O3S2-donor macrocyclic ligands with (L1) and without (L2) dibenzosubunit afforded respective exo- (1) and endo-coordinated (2) complexes depending on the ring rigidity of the ligands. From the X-ray crystal structures and comparative NMR studies for the complexes 1 and 2, it is confirmed that the resulting species with different coordination modes exist not only in solid state but also in solution state.

• 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.

• Bulletin of the Korean Chemical Society
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• v.21 no.7
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• pp.685-689
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• 2000

The complexation reaction between Pb2+,TI and Cd2+ions and macrocyclic ligands, 18-crown-6 ( 18C6) and dibenzo- 18-crown-6 (DB 18C6), was studied in dimethylsulfoxide (DMSO)-nitromethane (NM) and dimethyl-formamide (DMF)-nitromethane binary system s by square wave polarography (SWP) technique. The stoichiometry and stability of the complexes were determined by monitoring the shifts in half-waves or peak potentials of the polarographic waves of metal ions against the Iigand concentration. In most cases, the stability constants of complexes increase with increasing amounts of the nitromethane in mixed binary solvents used in this study. The complexes formed between 18C6 and DB18C6 and these metal cations in all cases had a stoichiometry of 1 : 1. The results obtained show that there is an inverse relationship between the formation constant of complexes and the donor number of solvents based on a Gatmann donocity scale and the stability constants show a high sensitivity to the composition of the mixed solvent systems. A linear behavior was observed for variation of log Kf of I8C6 complexes vs the composition of the mixed solvent systems in NM/DMSO and NM/DMF,but a non-linear behavior was observed in the case of DB 18C6 complexes in these binary systems. In most of the systems investigated, the Pb2+ cation forms a more stable complex with the 18C6 than other two cations and the order of selectivity of this Iigand for cations is: Pb2+ > TI+,Cd2+.

• Korean Journal of Crystallography
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• v.17 no.2
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• pp.41-45
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• 2006

The complex $cis-[Co(13-aneN_4)(N_3)_2]Cl\cdot H_2O$ (1) (13-ane$N_4$ = 1,4,7,10-tetraazacyclotridecane) has been synthesized and structurally characterized by X-ray crystalloaraphy. It crystallizes in the orthorhombic system Pbca, a = 7.8282(4) ${\AA}$, b = 14.3197(7) ${\AA}$, c = 29.9021(15) ${\AA}$, V = 3351.9(3) ${\AA}^3$, Z = 8. The cobalt(III) ion in 1 is coordinated to four nitrogen atoms from the macrocycle and two azide ligands of cis position in a distorted octahedral environment, which forms the 1D polymer through hydrogen bonding contacts involving the cation, chloride anion and solvent water molecules.

• Journal of the Korean Chemical Society
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• v.47 no.2
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• pp.104-108
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• 2003

The reaction of $[Cu(L)]Cl_2{\cdot}H_2O(L=3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0^{1.18},0^{7.12}]docosane)$ with 2,5-pyridinedicarboxylate(pdc) led to the formation of $[Cu(L)(H_2O)](pdc){\cdot}6H_2O(1)$. The structure was characterized by X-ray crystallography and spectroscopic method. The coordination geometry around the copper atom is a distorted square-pyramid with four secondary amines of the macrocycle occupying the basal sites and a water molecule at the axial position. Intermolecular hydrogen bonds in 1 form a three-dimensional molecular network.

• Bulletin of the Korean Chemical Society
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• v.12 no.2
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• pp.130-137
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• 1991

The following new cryptand 221 complexes of lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate have been synthesized: $(Ln(C_{16}H_{32}N_2O_5)(H_2O)_2(NO_3)_3\ and \((UO_2)_2(C_{16}H_{32}N_2O_5)(H_2O)_4(NO_3)_4$. These complexes have been identified by elemental analysis, moisture titration, conductivity measurements and various spectroscopic techniques. The proton and carbon-13 NMR as well as calorimetric measurements were used to study the interaction of cryptand 221 with La(Ⅲ), Pr(Ⅲ ), Ho(Ⅲ) and $UO_2(Ⅱ)$ ions in nonaqueous solvents. The bands of metal-oxygen atoms, metal-nitrogen atoms and O-U-O in the IR spectra shift upon complexation to lower frequencies, and the vibrational spectra ({\delta}NMN$) of metal-amide complexes in the crystalline state exhibit lattice vibrations below 300 $cm^{-1}$. The NMR spectra of the lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate complexes in nonaqueous solvents are quite different, indicating that the ligand exists in different conformation, and also the $^1H$ and $^{13}C-NMR$ studies indicated that the nitrogen atom of the ring has greater affinity to metal ions than does the oxygen atom, and the planalities of the ring are lost by complexation with metal ions. Calorimetric measurements show that cryptand 221 forms more stable complexes with $La^{3+}$ and $Pr^{3+}$ ions than with $UO^{22+}$ ion, and $La^{3+}/Pr^{3+}$ and $UO^{22+}/Pr^{3+}$ selectivity depends on the solvents. These changes on the stabilities are dependent on the basicity of the ligand and the size of the metal ions. The absorption band (230-260 nm) of the complex which arises from the direct interaction of macrocyclic donor atoms with the metal ion is due to n-{\delta}*$ transition and also that (640-675 nm) of $UO^{22+}$-cryptand 221 complex, which arises from interaction between two-dioxouranium(Ⅵ) ions in being out of cavity of the ligand ring is due to d-d* transition.

• Bulletin of the Korean Chemical Society
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• v.32 no.5
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• pp.1669-1678
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• 2011

Six new binuclear copper(II) complexes have been prepared by template condensation of the dialdehydes 1,8-[bis(3-formyl-2-hydroxy-5-methyl)benzyl]-l,4,8,11-tetraazacyclotetradecane (PC-a) and 1,8-[bis(3-formyl-2-hydroxy-5-bromo)benzyl]-l,4,8,11-tetraazacyclotetradecane (PC-b) with appropriate aliphatic diamines, and copper(II) perchlorate. The structural features of the complexes have been confirmed by elemental analysis, IR, UV-vis and mass spectra etc. The electrochemical behavior of all the copper(II) complexes show two irreversible one electron reduction process. The room temperature magnetic moment studies depict the presence of an antiferromagnetic interaction in the binuclear complexes. The catechol oxidation and hydrolysis of 4-nitrophenylphosphate were carried out by using the complexes as catalyst. The antimicrobial screening data show good results. The binding of the complexes to calf thymus DNA (CT DNA) has been investigated with absorption and emission spectroscopy. The complex [$Cu_2L^{1a}$] displays significant cleavage property of circular plasmid pBR322 DNA in to linear form. Spectral, electrochemical, magnetic and catalytic studies support the distortion of the copper ion geometry that arises as the macrocyclic ring size increases.

• 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.