• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2701-2704
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• 2010

This work shows that both L2 and L3 bearing two and four N-$(CH_2)_2OCH_3$ groups, respectively, can be prepared selectively by the reaction of $L^1$ with 1-bromo-2-methoxyethane. The di-N-substituted macrocycle $L^2$ readily forms its copper(II) and nickel(II) complexes. The N-$(CH_2)_2OCH_3$ groups in $[CuL^2]^{2+}$ are coordinated to the metal ion, whereas those in $[NiL^2]^{2+}$ are not involved in coordination. Interestingly, $L^3$ reacts with $Cu^{2+}$ ion to form $[Cu(HL^3)]^{3+}$, in which one tertiary amino group is not involved in coordination.

• Bulletin of the Korean Chemical Society
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• v.30 no.8
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• pp.1715-1718
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• 2009

A series of sitting-atop (SAT) complexes, [(ZrO)$H_2t(X)pp(NO_3)_2$], have been prepared via the reactions of free base meso-tetraarylporphyrins, $H_2$t(X)pp, with zirconyl nitrate hydrate, ZrO(N$O_3)_2{\cdot}xH_2$O. The products have been characterized by a variety of methods including $^1H\;NMR,\;^{13}C$ NMR, IR and UV-Vis spectroscopies, elemental analysis and conductance measurements. The data indicate that the meso-tetraarylporphyrins coordinate with two pyrrolenine nitrogen atoms to the zirconyl cation located above the distorted porphyrin plane and two protons remain on the pyrrole nitrogens. Such half sandwich-type sitting-atop complexes may be considered as models for the initial steps of the metallation of the macrocycles.

• Bulletin of the Korean Chemical Society
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• v.31 no.4
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• pp.815-818
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• 2010

Free base meso-tetraarylporphyrins ($H_2T(X)PP$) react with tellurium(IV) chloride ($TeCl_4$) in mild conditions for formation sandwich intermediate sitting-atop (i-SAT) complexes, [$TeCl_4(H_2T(X)PP)_2$]. $^1H$ NMR, $^{13}C$ NMR, UV-vis, FT-IR and elemental analysis were used for characterization of the products. In the proposed structure of the i-SAT complexes, four pyrroles of each porphyrin ring are tilted alternatively up and down and this appropriates suitable orientation of lone pairs of two pyrrolenine nitrogens for electron donation to a tellurium center. $^1H$ NMR and FT-IR results showed that in the produced complex, hydrogen atoms of porphyrin macrocycles remained on the pyrrole nitrogens.

• Bulletin of the Korean Chemical Society
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• v.18 no.6
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• pp.579-584
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• 1997

A series of ferrocene-containing chelating bidentate nitrogen ligands (1 & 2) and polyazamacrocycles (3 & 4) were prepared in high yields from the reaction of ferrocenecarboxaldehydes with corresponding diamines under various catalytic and stoichiometric reaction conditions. The stoichiometric condensation to form Schiff bases required the presence of MgSO₄in the reaction mixture as a water-absorbent. Employment of cyclic diamines such as 1,2-diaminocyclohexane and p-phenylenediamine in the reaction with 1,1'-ferrocenedicarboxaldehyde resulted in the formation of polymers in stead of the expected macrocycles. All these compounds were characterized by microanalytical and spectroscopic techniques. In one case, the structure of 3a was confirmed by X-ray crystallography.

• Bulletin of the Korean Chemical Society
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• v.13 no.3
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• pp.256-259
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• 1992

The 14-membered tetraaza macrocyclic ligand 1,8-diethyl-5,12-dimethyl-1,4,8,11-tetraazacyclote tradeca-4,11-diene(B) can be synthesized as its dihydroperchlorate salt by the one-pot reaction of 2-ethylaminoethylamine, methylvinyl ketone, and perchloric acid in absolute ethanol. The reaction of Ni(II) or Cu(II) ion and the salt yields $[M(B)]^{2+}$ (M = Ni(II) or Cu(II)), which reacts with $NaBH_4$ to produce $[M(D)]^{2+}$ (D = 1,8-diethyl-5,12-dimethyl-1,4,8,11-tetraazacyclote tradecane). The complexes $[M(L)]^{2+}$ (L = B or D) have planar geometry and contain two ethyl groups at the donor nitrogen atoms of the ligands. The red solids $[Cu(B)](X)_2(X)$ = $ClO_4-$ or $PF_6^-$) react with water molecules of atmospheric moisture to produce the purple solids in which water molecules are coordinated to the metal ion. Synthesis, characterization, and the properties of the new N-ethylated macrocyclic ligands and their Ni(II) and Cu(II) complexes are reported.

• The Korean Journal of Nuclear Medicine
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• v.39 no.4
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• pp.215-223
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• 2005

Current interest in the regioselective N-functionalization of tetraazacycloalkanes (cyclen and cyclam) stems mainly from their complexes with radioactive metals for applications in diagnostic ($^{64}Cu,\;^{111}In,\;^{67}Ga$) and therapeutic ($^{90}Y$) medicine, and with paramagnetic ions for magnetic resonance imaging ($Gd^{+3}$). Selective methods for the N-substitution of cyclen and cyclam is a crucial step in most syntheses of cyclen and cyclam-based radiometal complexes and bifunctional chelating agents. In addition, mixing different pendent groups to give hetero-substituted cyclen derivatives would be advantageous in many applications for fine-tuning the compound's physical properties. So far, numerous approaches for the regioselective N-substitution of tetraazacycloalkanes and more specifically cyclen and cyclam are reported. Unfortunately, none of them are general and every strategy has its own strong points and drawbacks. Herein, we categorize numerous regioselective N-alkylation methods into three strategies, such as 1) direct substitution of the macrocycle, 2) introductiou of the functional groups prior to cyclization, and 3) protection/iunclionallrationideproteclion. Our discussion is also split into the methods of mono- and tri-functionalization and di-functionalizataion based on number of substituents. At the end, we describe new trials for the new macrocycles which iorm more stable metal complexes with various radiometals, and briefly mention the commercially available tetraazacycloalkanes which are used for the biconjugation of biomolecules.

• Bulletin of the Korean Chemical Society
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• v.25 no.1
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• pp.85-89
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• 2004

Geometrical structures of [Pd(L)$Cl_2$] with oxathia macrocycles have been calculated using ab initio secondorder Moller-Plesset (MP2) and Density Functional Theory (DFT) methods with triple zeta plus polarization (TZP) basis set level. In optimized Pd(L)$Cl_2$ complexes, Pd(II) locates at the center surrounded by a square planar array of two sulfurs on an oxathia macrocycle and two chlorides. The endo-Pd(II) complexes with an axial (Pd${\cdots}$O) interaction are more stable than the exo-Pd(II) complexes without the interaction. In the endo-Pd(II) complexes, the atomic charge of the oxygen atom moves to Pd(II) via the axial ($Pd{\cdots}$O) interaction and then, the charge transfer from Pd(II) to the S-atoms occurs stepwise via ${\pi}$-acceptors of the empty d-orbitals.

• Bulletin of the Korean Chemical Society
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• v.11 no.6
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• pp.521-527
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• 1990

The binding characteristics and analytical applications of anilinium ion complexes with 18-crown-6 were studied by polarography and NMR. First, the electrochemical reduction of the 10 species of mono and dimethylsubstituted anilinium ion complexes with 18-crown-6 as host in methanol are examined. The addition of 18-crown-6 to anilinium guest solution the polarographic waves remain well defined but shifted toward more negative potentials, indicating the complex formation. The values of formation constants, log Κ for 10 species of methylsubstituted anilinium ion complexes with 18-crown-6 varies from 2.7 to 4.8 in methanol at $25^{\circ}C$. The stability order of complexes for 18-crown-6 is anilinilum > 4-methyl > 3,4-dimethyl > 3-methyl > 3,5-dimethyl > 2,4-dimethyl > 2,5-dimethyl > 2,3-dimethyl > 2-methyl > 2,6-dimethylanilinium ion. The steric hindrance shows significant effect. Second, Proton NMR was used to elucidate their interaction characteristics. From the results of so called NMR titration techniques, the behaviors of binding sites on complexation, and the stoichiometry and stability order of complex were obtained. And the later results show the satisfactory agreement with the quantitative values obtained by polarography. Finally, the individual determinations of anilinium ion mixtures were also accomplished by addition of 18-crown-6. In some mixtures of methyl or dimethylanilinium ions the reduction peaks of differential pulse method appeared into one unresolved wave attributed to the small difference of half-wave potential, ${\Delta}E_{1/2}$. In the presence of 18-crown-6, the polarographic waves were resolved into individual maxima because of the shift toward more negative direction by the difference of selectivity of anilinium ions with 18-crown-6. It may be concluded that quantitative analysis of methylanilinium ion mixture make possible because the half-wave potential shift by the selectivity difference due to the steric hindrance between methyl group and 18-crown-6 on complexation.

• Bulletin of the Korean Chemical Society
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• v.13 no.4
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• pp.363-367
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• 1992

The crystal structure of (1,3,6,9,11,14-hexaazatricycol[12.2.1.$1^{6,9}$]octadecane)copper(Ⅱ) perchlorate, Cu($C_{12}H_{26}N_6$)$(ClO_4)_2$, has been determined by the X-ray diffraction methods. The crystal data are as follows: Mr=516.9, triclinic, ${\alpha}=8.572\;(2)$, b=8.499 (3), c=15.204 (3) ${\AA}$, ${\alpha}=80.42\;(5),\;{\beta}=73.57\;(3),\;{\gamma}=69.82\;(4)^{\circ},\;V=994.2\;{\AA}^3,\;D_C=1.726\;gcm^{-3}$, space group $P{\tilde{1}},\;Z=2,\;{\mu}=21.27\;cm^{-1}&, F(000)=534 and T=297 K. The structure was solved by direct methods and refined by full-matrix least-squares methods to and R value of 0.081 for 1608 observed reflections measured with graphite-mono-chromated Mo Ka radiation on a diffractometer. There are two independent complexes in the unit cell. The two copper ions lie at the special positions (1/2, 0, 0) and (0, 1/2, 1/2)and each complex possesses crystallographic center of symmetry. Each Cu ion is coordinated to four nitrogen donors if the hexaazamacrotricyclic ligand and weakly interacts with two oxygen atoms of the perchlorate ions to form a tetragonally distorted octahedral coordination geometry. The Cu_N (sec), Cu_N(tert) and Cu_O coordination distances are 1.985 (14), 2.055 (14) and 2.757 (13) ${\AA}$ for the complex A and 1.996 (10), 2.040 (11) and 2.660 (13) ${\AA}$ for the complex B, respectively. The macrocycles in the two independent cations assume a similar conformation with the average r.m.s. deviation of 0.073 ${\AA}$. Two 1,3-diazacyclopentane ring moieties of the hexaazamacrotricyclic ligand are placed oppositely and almost perpendicularly to the square coordination plane of the ruffled 14-membered macrocycle. The secondary N atoms are hydrogen-bonded to the perchlorate O atoms with distances of 3.017 (23) and 3.025 (19) ${\AA}$ for the complexes A and B, respectively.

• Journal of Environmental Science International
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• v.4 no.2
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• pp.223-232
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• 1995

New two macrocyclic compounds using as carriers of liquid emulsion menbrame, have been synthesized. These reuslts provide evidance for the usefulness of the theory in designing the systems. The efficiency of selective transport for heavy metal ions have been discussed from the membrane systems that make use of $SCN^-$,<>,$I^-$,CN- and $Cl^-$ ion as co-anions in source phase and make use of $S_2O_3^{2-}$ and $P_2O_7^{4-}$ ion as receiving phase, respectively. The transport rate of M(II) was highest when a maximum amount of the M(II) in the source phase was present as$Cd(SCN)_2$$(P[SCN^-]= 0.40M)$, $Hg(SCN)_2([SCN^-]=0.40M)$ and Pd(CN)$([CN^-]= 0.40M)$. The Cd(II) and Pb(II) over each competitive cations were well transprted with 0.3M-S2032- and 0.3M-P2O74-, respectively in the receiving phase. Results of this study indicate that two criteria must be met in order to have effective macrocycle-mediated transport in these emulsion system. First one must effective extraction of the $M^{n+}$ into the toluene systems. The effectiveness of this extraction is the greatest if locK for $M^{n+}$macrocycle interaction is large and if the macrocycle is very insoluble in the aqueous phase. Second, the ratio of the locK values (or Mn+-receiving phase ($S_2O_3^{2-}$- or $P_2O_7^{4-}$) to $M^{n+}$-macrocycle (($L_1$이나 $L_2$) interaction must be large enough to ensure quantitative stripping of Mn+(($Cd^{2+}$,$Pb^{2+}$)at the toluene receiving Phase interface. $L_1$(3.5-benzo-10,13,18,21-tetraoxa-1,7,diazabicyclo(8,5,5) eicosan) forms a stable ($Cd^{2+}$ and >,$Pb^{2+}$ complexes and $L_1$ is very insoluble in water and its $Cd^{2+}$ and >,$Pb^{2+}$ complex is considerably less stable than $Cd^{2+}$-(S2O3)22- and $Pd^{2+}-P_2O_7^{4-}$ complexes. On the other hand, the stability of the $Hg^{2+}$)+-$L_1$( complex exceed that of the $Hg^{2+}$- (S2O3)22- and Hg2+-P2O74-, and the distribution coefficient of $L_2$(5,8,15,18,23,26-hexaoxa-1,12- diazabicyclo-(10,8,8) octacosane) is much smaller than that of $L_1$. Therefore, the partitioning of Lr is favored by the aqueous receiving Phase, and little heavy metal ions transport is seen despite the large logK for $Hg^{2+}$+-$L_1$ and $Mn^+$($Cd^{2+}$+, $Pb^{2+}$+ and $Hg^{2+}$)-$L_2$ interactions. Key Words : macrocycles, transport, heavy metal, co-anion, source phase, receiveing, complex separation, interaction, destribution coefficient.