• 한국결정학회지
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• 제9권1호
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• pp.11-14
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• 1998

[Cu(L)](NCS)2 (1) (L:2,5,9,12-Tetramethyl-1,4,8,11-tetraazacyclotetradecane) 착물을 합성하고 구조를 규명하였다. 이 착물은 단순결정, 공간군 P21/a, a=7.622(2)Å, b=17.645(2) Å, c=8.223(3) Å, β=109.99(2)˚, Z=2로 결정화 되었다. 이착물의 구조는 최소자승법으로 정밀화 하였으며, 최종 신뢰도 R(Rw)값은 1535개의 회석반점에 대하여 0.087및 0.158이었다. 이 착물의 결정구조는 Cu-N(이차 아민)의 평균 거리가 2.030(4)Å인 평면 사각구조를 갖는다. 축에 놓여있는 NCS-음이온은 Cu-N 거리가 2,842(7)Å로 결합되어 있지 않았다.

• 한국결정학회지
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• 제13권1호
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• pp.12-16
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• 2002

[Ni(L)](BDC)·4H₂O (1) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[16,4,O/sup 1.18/,O/sup 7.12/]docosane;BDC = 1,3-benzenedicarboxylate) 착물을 합성하고 구조를 규명하였다. 이 착물은 사방정계, 공간군 Pcnb, a = 8.764(2) , b = 17.687(2) , c = 19.475(1) , V = 3018.7(8) ³, Z = 4로 결정화 되었다. 이 착물의 구조는 최소자승법으로 정밀화하였으며, 최종 신뢰도 R₁(wR₂)값은 2148개의 회절반점에 대하여 0.0822 및 0.2236이었다. 화합물 1은 수소결합들로 연결된 삼차원의 그물 구조를 갖는다.

• 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.

• Bulletin of the Korean Chemical Society
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• 제21권11호
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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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• 제21권7호
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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+.

• 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.

• 대한화학회지
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• 제29권2호
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• pp.151-157
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• 1985

클로로포름 용액에서 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane(cryptand 22), 1,7-diaza-4,10,13-trioxacyclopentadecane(cryptand 21), 1,12,15-triaza-5,8-dioxa-3,4:9,10-dibenzocycloheptadecane ($N_3O_2$) 및 1,12-diaza-5,8-dioxa-3,4:9,10-dibenzocyclotetradecane ($N_2O_2$)의 분자간 수소결합을 $^1H$-nmr 분광법으로 여러 온도에서 조사하였다. 묽은 용액에서 이 화합물들은 -NH기를 통한 수소결합에 의하여 이합체를 형성한다. 수소결합형성에 대한 평형상수 값의 크기는 cryptand 22 > cryptand 21 > $N_3O_2$ > $N_2O_2$의 순위이었다. 이 평형에는 분자구조의 대칭성과 분자내의 -NH기의 수와 위치가 영향을 미치고 있었다.

• Bulletin of the Korean Chemical Society
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• 제32권5호
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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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• 제25권2호
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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.

• 환경위생공학
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• 제15권1호
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• pp.25-33
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• 2000

1%, 2%, 10%, 및 20%의 가교도를 갖는 클로로메틸화된 1,4-divinyl benzene에 1-aza-15-crown-5 거대고리 ligand를 치환반응으로 결합시키고, 이들 수지로부터 흡착에 미치는 pH, 시간, 수지의 가교도 그리고 용매의 유전상수 크기에 따른 흡착특성을 조사하였다. 금속이온들은 pH 4 이상에서 우라늄과 칼슘 이온들은 루테튬 이온보다 큰 흡착률을 보였으며, 금속이온들의 흡착 평형시간은 약 2 시간이었다. 한편, ethanol 매질에서의 흡착선택성은 $UO_2^{2+}>Ca^{2}>Lu^{3+}$ 이었고, 흡착력은 1%, 2%, 10%, 20%의 가교도 순 이었으며, 용매의 유전상수(물 : 78.54, 메탄올 : 32.63, 에탄올 : 24.30) 크기에 반비례하였다. 컬럼에서 1%의 가교도를 가진 수지와 금속이온들을 흡착시킨 후 용리액으로 pH2.5 $HNO_3$을 사용하여 각각 분리할 수 있었다.