• 분석과학
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• 제8권4호
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• pp.449-456
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• 1995

Novel macrocyclic ligands modified with pendant arms, N, N', N'', N''', N'''', N'''''-hexakis(2-aminoethyl)-1, 4, 7, 10, 13, 16-hexaazacyclootadecane [$L_3$, Fig.1] and 1, 4, 7-tris(3-(o-hydroxyphenyl)propyl)-1, 4, 7-triazacyclononane [$L_4$, Fig.1] have been synthesized, and the protonation of $L_3$ and $L_4$ and stability constants of $L_3$ with bivalent transition metal ions and rare earth metal ions were determined by a potentiometry. The obtained results show that the complex formation of $L_3$ depends on the metal ligand ratios, and the stability of the metal complexes does not depend on the sizes of the metal ions, but on the nature of the metal ions. The structures of the rare earth complexes for $L_4$ were characterized by an X-ray absorption spectrometry(XAFS).

• Bulletin of the Korean Chemical Society
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• 제31권12호
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• pp.3707-3710
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• 2010

A chromo/fluorogenic $NO_2S_2$-macrocycle L functionalized with nitrobenzofurazan unit as a dual-signaling probe was synthesized and structurally characterized by single crystal X-ray analysis. In a cation-induced color change experiment, L exhibited excellent $Hg^{2+}$ ion selectivity by showing the color change from orange-red to yellow. However, this hypochromic shift by $Hg^{2+}$ was observed for the weaker coordinating anion system such as ${NO_3}^-$ and ${ClO_4}^-$ ions. The observed anion effect is due to the strong coordination of anions inhibits the bond formation between $Hg^{2+}$ and the macrocyclic tert-N atom, which is sensitive to induce the color change. In the fluorometric experiment, L showed chelate-enhanced fluorescence change effect only with $Hg^{2+}$ ion, together with a change from yellow to green emission. The sensing ability for $Hg^{2+}$ with the proposed chemosensor L is due to the stable complexation with 1:1 stoichiometry (metal-to-ligand).

• 대한화학회지
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• 제31권6호
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• pp.503-508
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• 1987

3,4 : 9,10-dibenzo-1,12-diaza-5,8-dioxacyclotetradecane $(NenOenH_4)$과 전이금속이온$(Cu^{2+},\;Ni^{2+},\;Co^{2+},\;Zn^{2+},\;Mn^{2+})$과의 착물의 안정도상수를 50%다이옥산-수용액에서 이온강도를 0.1로 하고, 전위차법적정으로 측정한 결과, 전이금속이온과 리간드가 만드는 착물의 안정도상수의 순서는 Williams-Irving서열과 일치한다.

• 대한화학회지
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• 제35권6호
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• pp.645-652
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• 1991

몇 가지 전이금속이온(Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ)) 및 후전이금속이온(Cd(Ⅱ), Hg(Ⅱ), Pb(Ⅱ))과 $N_2O_3$계 거대고리 리간드인 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane 사이에 형성되는 착물의 안정도 상수를 수용액에서 전위차 적정법으로 결정하였다. 각 착물의 안정도 상수$(logK_f)$는 $25^{\circ}$C에서 Co(Ⅱ): 3.83, Ni(Ⅱ) : 4.56, Cu(Ⅱ) : 7.74, Zn(Ⅱ) : 4.98, Cd(Ⅱ) : 3.91, Hg(II) : 14.87, Pb(Ⅱ) : 6.65이었다. 전이금속착물의 안정도 순위는 Williams-Irving 서열인 Co(Ⅱ) < Ni(Ⅱ) < Cu(Ⅱ) < Zn(Ⅱ)와 일치하였고, 후전이금속착물의 안정도는 Cd(Ⅱ) < Pb(Ⅱ) < Hg(Ⅱ)이 순위이었다. 한편 메탄올 용액에서 자외-가시선이온과 리간드가 1:1인 조성을 가졌으나, Ni(Ⅱ), 착물은 1:1과 1:2 두 가지 조성을 가질 수 있음을 알았으며, 또 디메틸술폭시드 용액에서 $^1H-$와 $^{13}C-$핵자기공명스펙트럼을 분석하여 후전이금속이온 착물은 주로 리간드의 질소원자가 결합에 기여함을 알았다. Cu(Ⅱ)와 Zn(Ⅱ)이 고체착물은 원소분석, 전기전도도, 자화율 측정, 자외-가시선 및 적외선 스펙트럼분석 등으로 Cu(Ⅱ) 착물은 일그러진 팔면체, 그리고 Zn(Ⅱ) 착물은 사면체 구조를 이루고 있는 것으로 예측되었다.

• Bulletin of the Korean Chemical Society
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• 제14권4호
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• pp.439-444
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• 1993

The aerobic oxidation of the Fe(II) complex of 1,4,8,11-tetraazacyclotetradecane, [Fe(cyclam)$(CH_3CN)_2](ClO_4)_2$, in MeCN in the presence of a few drops of $HClO_4$ leads to low spin Fe(III) species [Fe(cyclam)$(CH_3CN)_2](ClO_4)_3$. The Fe(III) cyclam complex is further oxidized in the air in the presence of a trace of water to produce the deep green binuclear bismacrocyclic Fe(II) complex $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$. The Fe(II) ions of the complex are six-coordinated and the bismacrocyclic ligand is extensively unsaturated. $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$ crystallizes in the monoclinic space group $P2_1/n$ with a= 13.099 (1) ${\AA}$, b= 10.930 (1) ${\AA}$, c= 17.859 (1) ${\AA}$, ${\beta}$= 95.315 $(7)^{\circ}$, and Z= 2. The structure was solved by heavy atom methods and refined anisotropically to R values of R= 0.0633 and $R_w$= 0.0702 for 1819 observed reflections with F > $4{\sigma}$ (F) measured with Mo K${\alpha}$ radiation on a CAD-4 diffractometer. The two macrocyclic units are coupled through the bridgehead carbons of ${\beta}$-diimitie moieties by a double bond. The double bonds in each macrocycle unit are localized. The average bond distances of $Fe(II)-N_{imine}$, $Fe(II)-N_{amine}$, and $Fe(II)-N_{MeCN}$ are 1.890 (5), 2.001 (5), and 1.925 (6) ${\AA}$, respectively. The complex is diamagnetic, containing two low spin Fe(II) ions in the molecule. The complex shows extremely intense charge transfer band in the near infrared at 868 nm with ${\varepsilon}$= 25,000 $M^{-1}cm^{-1}$. The complex shows a one-electron oxidation wave at +0.83 volts and two one-electron reduction waves at -0.43 and-0.72 volts vs. Ag/AgCl reference electrode. The complex reacts with carbon monoxide in $MeNO_2$ to form carbonyl adducts, whose $v_{CO}$ value (2010 $cm^{-1}$) indicates the ${\pi}$-accepting property of the present bismacrocyclic ligand.

• 한국결정학회지
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• 제17권2호
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• pp.41-45
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• 2006

[ $cis-[Co(13-aneN_4)(N_3)_2]Cl{\cdot}H_2O$ ] (1) (13-ane$N_4$ = 1,4,7,10-tetraazacyclotridecane) 착물(錯物)을 합성(合成)하고 구조(構造)를 규명(糾明)하였다. 이 착물(錯物)은 단사정계(單斜晶系), 공간군(空間群) Pbca, a = 7.8282(4) ${\AA}$, b = 14.3197(7) ${\AA}$, c = 29.9021(15) ${\AA}$, V= 3351.9(3) ${\AA}^3$, Z = 8로 결정화(決定化) 되었다. 착물(錯物) 1의 코발트(III)이온은 거대(巨大)고리 리간드의 4개(個)의 질소원자(窒素原子)와 시스 위치에 2개(個)의 azide 리간드가 결합(結合)한 고천(若干) 일그러진 팔면체(八面體) 구조(構造)를 갖는데, 착물(錯物)의 양이온, 염소(鹽素) 음이온 및 물분자(分子)를 통하여 1차원의 수소결합(水素結合)을 형성(形成)한다.

• Bulletin of the Korean Chemical Society
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• 제34권3호
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• pp.725-730
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• 2013

An investigation of the coordination behavior of sulfur-containing mixed-donor tribenzo-macrocycles $L^1-L^3$ ($L^1$: 20-membered $O_3S_2$, $L^2$: 20-membered $O_2S_3$, and $L^3$: 23-membered $O_4S_2$) with $d^{10}$-metal ($Ag^+$, $Hg^{2+}$, and $Pb^{2+}$) salts is reported. The X-ray structures of five complexes (1-5) with different structural types and stoichiometries, including mono- to dinuclear species have been determined. Reactions of $L^2$ and $L^3$ with the silver(I) salts ($PF_6{^-}$ and $SCN^-$) afforded two dinuclear 2:2 (metal-to-ligand) complexes with different arrangements: a sandwich-type cyclic dinuclear complex $[Ag_2(L^2)_2](PF_6)_2{\cdot}3CH_2Cl_2$ (1) and a linear dinuclear complex $[Ag_2(L^3)_2(SCN)_2]$ (2), in which two monosilver(I) complex units are linked by an Ag-Ag contact. Reactions of $L^1$ and $L^2$ with mercury(II) salts ($SCN^-$ and $Cl^-$) gave a mononuclear 1:1 complexes $[Hg(L^1)(SCN)_2]$ (3) and $[Hg(L^2)Cl_2]$ (4) with anion coordination in both cases. $L^2$ reacts with lead(II) perchlorate to yield a mononuclear sandwich-type complex $[Pb(L^2)_2(ClO_4)_2]$ (5), giving an overall metal coordination geometry of eight with a square antiprism arrangement. From these results, the effects of the donor variation and the anioncoordination ability on the resulting topologies of the soft metal complexes are discussed.

• 한국결정학회지
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• 제10권1호
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• pp.33-38
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• 1999

The complex [Ni(L2)(H2O)]Cl·H2O (1) (L2=3,14-dimethyl-2,6,13,17-tetraazartricyclo [14,4,01.18,07.12]docosane-N-acetic acid) has been synthesized and characterized by X-ray crystallography. 1 crystallizes in the triclinic system, space group P, with a=11.274(1), b=13.851(1), c=17.159(6) , α=90.24(2), β=101.10(2), γ=92.11(1)o V=2682.5(11) 3, Z=4, R1=0.042 and wR2=0.111 for 9432 observed reflections with [I>2σ(I)]. The central nicke(II) ion is six-coordinated octahedral geometry with bonds to the four amine nitrogen atoms the carboxylic oxygen atom of the macrocyclic ligand and to the water molecule occupying a position trans to the pendant arm.

• 멤브레인
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• 제24권6호
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• pp.472-483
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• 2014

본 연구는 거대고리 금속 이온 착화합물과 유도체를 이용하여 미세 다공성 구조를 가지는 분리막의 제조에 관한 것이다. 고분자와 금속이온 리간드 착물 시스템을 이용함으로써 기존의 방법들에 비해 상 전이 과정을 보다 정교하게 제어할 수 있었다. 금속염, cyclohexanedione dioxime, hydroxyphenylboronic acid와의 축합 반응을 통하여 금속 clathrochelate 착물을 얻을 수 있었다. PES, PVP, BE와 금속 clathrochelate 착물을 DMF에 녹인 후 비용매 유도 상 전이법을 통하여 유무기 혼성고분자막을 제조하였다. 제조된 분리막의 구조는 FE-SEM과 microflow permporometer로 조사하였다. p-Hydroxyphenyl group을 가지는 Fe(II) clathrochelate 착물의 첨가는 분리막의 구조에 있어 기공 크기 분산도를 좁혀주고, 표면의 기공 밀도를 높여 주었으며 최대 기공 크기를 감소시킴을 볼 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제17권9호
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• pp.790-793
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• 1996

The azacrown compound, 1,7-dioxa-4,10,13-triazacyclopentadecane-N,N',N"-tri(methyl-acetic acid)(N3O2-tri(methylacetic acid)) was synthesized by modified procedure of Krespan. Potentiometric method has been used to determine the protonation constants of N3O2-tri(methylacetic acid) and stability constants of complexes on the divalent transition metal ions (Co2+, Ni2+, Cu2+, and Zn2+) and trivalent metal ions (Ce3+, Eu3+, Gd3+, and Yb3+) with N3O2-tri(methylacetic acid). The stability constants for the complexes of the divalent transition metal ions studied in the present work with N3O2-tri(methylacetic acid) were 11.4 for Co2+, 11.63 for Ni2+, 13.51 for Cu2+, and 11.65 for Zn2+, respectively. Thus, the order of the stability constants for complexes on the transition metal ions with N3O2-tri(methylacetic acid) was shown Co2+ < Ni2+ < Cu2+ > Zn2+ as same as the order of Irving-Williams series. The stability constants of Ce3+, Eu3+, Gd3+, and Yb3+ trivalent lanthanide metal ion complexes of N3O2-tri(methylacetic acid) were, respectively, 11.26 for Ce3+, 11.56 for Eu3+, 11.49 for Gd3+, and 11.80 for Yb3+. The values of the stability constants on trivalent metal ions with the ligand are increasing according to increase atomic number, due to increase acidity. But the value of stability constant of Gd3+ ion is less than the value of Eu3+ ion. This disordered behavior is also reported by Moeller.