• Bulletin of the Korean Chemical Society
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• 제25권1호
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• pp.37-41
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• 2004

A new tridentate ligand incorporating a monoxime and thiosemi-carbozone moieties has been synthesized. Its copper(II), nickel(II) and palladium(II) complexes have been prepared and characteirzed by physical and spectral methods. Elemental analyses and spectroscopic data of the metal complexes are consistent with the formation of a mononuclear copper(II) complex and binuclear complex with both nickel(II) and palladium(II). In the copper(II) complex the fourth coordination site is occupied by nitrate ion. In the binculear complexes the fourth coordination site is occupied by the deprotonated oxime oxygen of the ligand coordinated to the other metal.

• Bulletin of the Korean Chemical Society
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• 제33권7호
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• pp.2279-2286
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• 2012

The template synthesis of copper(II) and nickel(II) complexes derived from 2,6-diformyl-4-methylphenol with diethylenetriamine or 1,2-bis(3-aminopropylamino)ethane produce the 12-membered $N_3O$ and 17-membered $N_4O$ macrocyclic complexes, respectively. The geometry of the complexes has been determined with the help of electronic and EPR spectroscopic values and found to be five coordinated square pyramidal and, six coordinated distorted tetragonal for 12-membered and 17-membered macrocyclic complexes, respectively. Electrochemical studies of the mononuclear $N_3O$ and $N_4O$ copper(II) complexes show one irreversible oneelectron reduction wave at $E_{pc}=-1.35$ and -1.15 V respectively, and the corresponding nickel(II) complexes show irreversible one-electron reduction wave at $E_{pc}=-1.25$ and -1.22 V, respectively. The nickel(II) complexes show irreversible one-electron oxidation wave at $E_{pa}=+0.84$ and +0.82 V, respectively. All the complexes were evaluated for in vitro antimicrobial activity against the human pathogenic bacteria and fungi.

• 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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• 제15권5호
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• pp.374-378
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• 1994

Square planar nickel(II) complexes with various 1-alkyl derivatives of the 14-membered pentaaza macrocycle 8-methyl-8-nitro-1,3,6,10,13-pentaazacyclotetradecane can be readily prepared by two-step metal template condensation reactions of ethylenediamine, nitroethane, formaldehyde, and appropriate primary alkylamines. In coordinating solvents the nickel (II) complexes form octahedral species containing two axially coordinated solvent molecules and thus show square planar-octahedral equilibrium. The properties of the pentaaza macrocyclic complexes are considerably different from those of the complexes of analogous hexaaza and tetraaza macrocyclic complexes. Synthesis, characterization, and spectroscopic and chemical properties of the new complexes are described.

• 대한화학회지
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• 제55권2호
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• pp.189-198
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• 2011

두 가지 새로운 thiosemicarbazone으로, 예를 들면, 4[N-(4'-ethylbenzalidene)amino]antipyrine thiosemicarbazone(EBAAPTS) 및 4[N-(2',4'-dimethylbenzalidene)amino]antipyrine thiosemicarbazone(DMBAAPTS)를 합성하여 그 특성을 규명하였다. 이들 thiosemicarbazone(EBAAPTS 및 DMBAAPTS)의 코발트(II) 및 니켈(II)에 대한 착물화 특성을 조사하였다. EBAAPTS 및 DMBAAPTS와 코발트(II) 및 니켈(II) 염과의 반응을 뜨거운 에탄올 용액에서 수행한 결과, 일반적 조성으로 [$MX_2(L)H_2O$] (M=$Co^{2+}$ 또는 $Ni^{2+}$; X=$Cl^-$, $Br^-$, $NO_3^-$, $NCS^-$ 또는 $CH_3COO^-$; L=EBAAPTS 또는 DMBAAPTS)을 갖는 새로운 착물의 형성을 확인하였다. 새롭게 합성한 이들 착물에 대해 원소분석, 분자량, 몰전도도, 자기수자율, 적외선 및 자외선 분광학 등의 방법으로 특성을 규명하였다. 니트로벤젠 용액에서 이들 착물의 몰전도도를 측정한 결과, 비전해질 성질을 가짐을 알았다. 또한, 모든 착물은 높은-스핀 형태였다. 분광학적 연구로부터 [$MX_2(L)H_2O$] 형의 코발트(II) 및 니켈(II) 착물은 팔면체의 기하구조를 갖는 것으로 확인되었다. 이들 착물을 이용하여 항박테리아 및 항균 활성을 여러 종류의 병원균, 세균 및 박테리아에 대해 조사하여 생물학적 활성을 고찰하였다.

• Bulletin of the Korean Chemical Society
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• 제25권12호
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• pp.1757-1763
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• 2004

A new series of nickel(II), cobalt(II)/(III) and copper(II) complexes of 14, 15 and 16-membered of macrocyclic ligands have been prepared and characterized by elemental analyses, IR, UV-VIS and $^1H-NMR$ spectra, magnetic susceptibilities, conductivities, DTA and ESR measurements. Molar conductances in DMF solution indicate that, the complexes are nonelectrolytes except (9-12) complexes. The electronic spectra show that, all complexes are square planar or distorted octahedral geometry. The ESR spectra of solid complexes (4), (8) and (11) show square planar of axial type symmetry $(d_{x2-y2})$ with considerable covalent bond character. However, complex (12) shows a spectrum of octahedral geometry with $d_{z2}$ ground state. Complex (12) shows exploitation in reducing the amount of electron adducts formed in DNA during irradiation with low radiation products.

• 분석과학
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• 제10권4호
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• pp.246-255
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• 1997

산소-질소계를 포함하는 여러 자리 시프염기 리간드인 비스-살리실알데히드-에틸렌디아민(SED), 비스-살리실알데히드-프로필렌디아민(SPD), 비스-살리실알데히드-디에틸렌트리아민(SDT) 및 비스-살리실알데히드-트리에틸렌테트라아민(STT)들과 니켈(II) 착물을 합성하여 원소분석법, 적외선분광법, 자외-가시흡광분광법 및 질량분석법을 이용하여 확인하였다. 이들 리간드를 70% 디옥산-30% 물 혼합 용매 및 에탄올 용매에서 전위차법으로 니켈(II)-시프염기 착물들의 안정도상수값을 각각 구하였다. 안정도상수값의 크기는 Ni(II)-SPD

• Bulletin of the Korean Chemical Society
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• 제14권5호
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• pp.594-598
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• 1993

The protonation constants of the 14-membered tetraaza macrocycles A(3,14-dimethyl-2,6,13,17-tetraazatricyclo$[l6.4.0^{1,18}.0^{7,12}]$docosane) and B(2,3,6,13,14,17-hexamethyl-2,6,13,17-tetraazatric yclo-[l6.4.$0^{1,18}.0^{7,12}$]docosane) were measured by potentiometry. The formation constants of each of these ligands with copper(II) and nickel(II) were determined by an out-of-cell spectrophotometric method. The results indicate that the per-N-methylated macrocycle B exhibits much higher selectivity for complex formation with copper(II) over nickel(II) ion than A and other related 14-membered tetraaza macrocycles. The effects of the N-and C-substituents on the basicity and the metal ion selectivity of the ligands are discussed. The synthesis and properties of copper(II) and nickel(II) complexes of B are also described.

• 대한화학회지
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• 제36권5호
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• pp.709-719
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• 1992

이핵성 네자리 Schiff base 의 cobalt(II), nickel(II) 및 copper(II) 착물인 [Co(II)_2(TSBP)(L)_4], [Ni(II)_2(TSBP)(L)_4] 및 [Cu(II)_2(TSBP)] (TSBP: 3,3',4,4'-tetra(salicylideneimino)-1,1'-biphenyl, L: Py, DMSO 및 DMF)들을 합성하여 원소분석, IR-spectrum, UV-visible spectrum, T.G.A. 및 D.S.C.를 측정하여 이핵성 착물로 주어짐을 확인하였다. 지지전해질로서 0.1M TEAP-L (L; Py, DMSO 및 DMF)에서 1mM-착물용액의 순환전압-전류법과 D.P.P.법으로 전기화학적 성질을 측정한 결과 이핵성 cobalt(II) 착물은 일전자의 확산 지배적인 네단계의 산화-환원과정이 Co(III)_2 {^\longrightarrow \\_\longleftarrow^e^-}Co(III)Co(II)_2{^\longrightarrow \\_\longleftarrow^e^-}Co(II){^\longrightarrow \\_\longleftarrow^e^-}Co(I){^\longrightarrow \\_\longleftarrow^e^-}Co(I)_2 으로 일어나고 이핵성 nickel(II) 및 copper(II) 착물들은 일전자의 확산지배적인 두 단계의 산화-환원과정이 M(II)_2 {^\longrightarrow \\_\longleftarrow^e^-}M(I)M(I){^\longrightarrow \\_\longleftarrow^e^-}M(I)_2 (M; Ni 및 Cu)으로 일어남을 알았다.

• Bulletin of the Korean Chemical Society
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• 제28권6호
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• pp.1053-1056
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• 2007