• Bulletin of the Korean Chemical Society
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• 제32권11호
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• pp.4117-4120
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• 2011

• Bulletin of the Korean Chemical Society
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• 제32권8호
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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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• 제28권4호
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• pp.589-595
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• 2007

The conversion of both the racemic and resolved forms of the Co(III) complex of an hydroxymethyl-substituted tripodal hexamine to macrobicycles via reaction with formaldehyde and nitromethane (and subsequent reduction of the product) has been conducted. The prospect is that it will provide cage complexes in which the hydroxyl substituent is sufficiently remote from the metal ion centre for its nucelophilicity to be largely unaffected. X-ray structure determinations have been used to characterise these new cage species as well as some complexes of the precursor hexamine and its mono-aminal. The electrochemistry and optical activity of the complexes have also been studied in detail.

• 대한핵의학회지
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• 제39권4호
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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.

• 대한화학회지
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• 제36권6호
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• pp.914-918
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• 1992

이 연구에서는 중성거대고리리간드를 운반체로 이용한 Emulsion 액체막에서 금속이온의 이동현상에 관하여 다루었다. Emulsion 막은 (1) 0.001M $M(NO_3)_2$ (M = $Mn^{2+}$, $Co^{2+}$, $Ni^{2+}$, $Cu^{2+}$, $Zn^{2+}$, $Sr^{2+}$, $Cd^{2+}$, $Pb^{2+}$)으로 된 수용액의 source phase와 (2)0.02M 거대고리리간드와 계면활성제인 span 80을 포함하는 toluene 막과 (3) $Na_2S_2O_3$ 또는 $NaNO_3$을 포함하는 receiving phase로 되어 있으며 시간에 따라 source phase로부터 금속이온들의 이동량을 연구하였다. 이성분계의 금속이온의 이동속도를 관찰하였다. 혼합용액에서의 $Cd^{2+}$이 다른 이온보다 높은 이동율을 나타내었다.

• Bulletin of the Korean Chemical Society
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• 제13권4호
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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.