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수용액에서 tetraaza macrocycle과 결합된 Ni(Ⅱ) 착물의 스핀 평형
고광오 순천향대학교 기초과학연구소 1999 순천향자연과학연구 논문집 Vol.5 No.1
Spin equilibrium of Ni(Ⅱ) complexes of 14- and 15-membered macrocyclic ligand (1,4,8,11-tetraazacyclotetradecane, 1,4,8,12-tetraazacyclopentadecane) were investigated using the spectro-scopic method. Macrocyclic ligands were purified by recrystallization. Formation of the low spin form is favoured with the ligand(1,4,8,11-tetraazacycloteradecane). Equilibrium constants of Ni(1,4,8,11-tetraazacyclotetradecane)Cl₂solution by the variation of ionic strength increase largely above 45℃. And high %(95%>) of the blue to yellow conversion in aqueous Ni(1,4,8,11-tetraazacyclotetradecane)Cl₂solution is possible above 60℃. Above I=3 mol ??, the equilibrium constants of Ni(1,4,8,11-tetraazacyclotetradecane)Cl₂solution by the variation of temperature increase largely.
고광오,정환 순천향대학교 기초과학연구소 2006 순천향자연과학연구 논문집 Vol.12 No.1
In this research, the structure and coordination state of Ni(Ⅱ) complexes with some ligands were investigated by spectroscopy method. [Ni(H₂O)_(6))]^(+2) and [Ni(1,4,8,12-tetraazacyclopentadecane) ]^(+2) show the octahedral complex at near 400 nm. [Ni(1,4,8,11-tetraazacyclotetradecane)]^(+2) shows the square complex (spin-paired diamagnetism) at 451 nm. When the 2-hydroxy-N-methylsuccinimide was added in [Ni(H₂O)_(6))]^(+2), there was no ligand exchange. In [NiL(H₂O)_(2))]^(+2) ⇔ [NiL]^(+2)+2H₂O, the equilibrium moved to right by temperature increase and electrolyte. The spectrochemical series of Ni^(+2) by solvents were studied by spectroscopy method.
Acetonitrile 용액에서 tetra aza macrocycle의 Zn(Ⅱ) 착물
고광오 순천향대학교 기초과학연구소 2001 순천향자연과학연구 논문집 Vol.7 No.1
Ligand 1,4,8,12-tetraazacyclopentadecane(base) was recrystallized. The reaction of 1,4,8,12-tetraazacyclopentadecane with ZnCl2 in acetonitrile solution has been studied conductimetrically. With equivalent amounts of base and ZnCl2, the reaction product is ZnCl2(base). The data for 1:1 solutions of base: Zn represent 10% ionization in 2×10-3 M ZnCl2. The molar conductivity of a solution with base:Zn ratio 1:2 was about half that expected for a 1:1 electrolyte, consistent with the formulation of the species in solution as [ZnCl(base)][ZnCl3].
수용액에서 tetraaza macrocycles과 Ni(Ⅱ) 착화합물의 구조
고광오 순천향대학교 기초과학연구소 1995 순천향자연과학연구 논문집 Vol.1 No.1
Structures of Ni(Ⅱ) complexes of 14- and 15-membered macrocyclic ligand (1,4,8,11-tetraazacycloteradecane, 1,4,8,12-tetraazacyclopentadecane) were investigated using the spectroscopic method and conductivity measurement. Macrocyclic ligands were purified by recrystallization method. On addition of macrocyclic ligands to the aqueous NiCl₂solution, the conductivity decreased steadily to a base:metal ion ratio of 1:1 and increased smoothly. This is due to the hydroxide ion by basic ligand(tetraaza macrocycles). By slope of the conductivity, 1,4,8,11-tetraazacyclotetradecane is more basic than 1,4,8,12-tetraazacyclopentadecane. According to the U.V. spectra, Ni(1,4,8,11-tetraazacyclotetradecane)Cl₂shows the square plane structure and Ni(1,4,8,12-tetraazacyclopentadecane)Cl₂is the distorted octahedral structure in aqueous solution.
용액에서 Ni(Ⅱ)이온과 functionalized 치환체를 포함하는 tetraaza 거대고리 리간드의 착물
고광오 순천향대학교 기초과학연구소 2004 순천향자연과학연구 논문집 Vol.10 No.2
Ligands NN'N''N'''-tetra(2-cyanoethyl)-1,4,8,11-tetraazacyclotetradecane(ligand 1) and NN'N''N'''-tetra(2-cyanoethyl)-1,4,8,12-tetraazacyclopentadecane(ligand 2) were synthesized. The reactions of ligand 1 and ligand 2 with NiCl₂, the reaction product is [Ni(ligand)*(H₂O)Cl]. The molar conductivities of a solutions with ligand:Ni ratio 1:1 were 97.7 Scm^(2)mol^(-1)(ligand 1) and 135.4 Scm^(2)mol^(-1)(ligand 2).
용액에서 Zn(Ⅱ)이온과 tetraaza 거대고리 리간드의 착물
고광오 순천향대학교 기초과학연구소 2002 순천향자연과학연구 논문집 Vol.8 No.1
Ligands 1,4,8,12-tetraazacyclotetradecane(base1) and 1,4,8,12-tetraazacyclotetradecane(base2) were recrystallized. The reactions of 1,4,8,11-tetraazacyclotetradecane(base1) and 1,4,8,12-tetraazacyclotetradecane with ZnCl_(2)in aqueous solution have been studied conductimetrically. With equivalent amounts of base and ZnCl_(2), the reaction product is ZnCl_(2)(base). The molar conductivities of a solutions with base:Zn ratio 1:1 were about two thirds that expected for a 2:1 electrolyte.
수용액에서 Cu(1,4,8,11-tetraazacyclotetradecane)Cl₂와 Cu(1,4,8,12-tetraazacyclopentadecane)Cl₂의 구조
고광오 순천향대학교 기초과학연구소 2000 순천향자연과학연구 논문집 Vol.6 No.1
Structures of Cu(II) complexes of 14- and 15-membered macrocyclic ligand (1,4,8,11-tetraazacycloteradecane, 1,4,8,12-tetraazacyclopentadecane) were investigated using the spectroscopic method and conductivity measurement. Macrocyclic ligands were purified by recrystallization method. On addition of macrocyclic ligands to the aqueous CuCl2 solution, the conductivity decreased steadily to a base:metal ion ratio of 1:1 and increased smoothly. This is due to the hydroxide ion by basic ligand(tetraaza macrocycles). By slope of the conductivity, 1,4,8,11-tetraazacyclotetradecane is more basic than 1,4,8,12-tetraazacyclopentadecane.According to the U.V. spectra, Cu(1,4,8,11- tetraazacyclotetradecane )Cl2 and Cu(1,4,8,12-tetraazacyclopentadecane) Cl2 show the distorted octahedral structure in aqueous solution.
Pendant functional group이 있는 cyclam 배위자의 Ni(Ⅱ) 착물
고광오 순천향대학교 기초과학연구소 1998 순천향자연과학연구 논문집 Vol.4 No.1
Nickel(Ⅱ) complexes of the ligands 1,4,8,11-tetrakis(2-cyanoethyl)-1,4,8,11-tetra-azacyclotetra- decane(E) and 1,4,8,11-tetrakis(2-carbamoylethyl)-1,4,8,11-tetra-azacyclotetradecane (F) were synthesized. Heating ?? in water resulted in formation of a complex of 1,8-bis(2-carbamoylethyl)-4-(2-cyanoethyl)-1,4,8,11-tetraazacyclotetradecane(G). [Ni(G)](ClO₄)₂shows it to contain a six-coordinate nickel ion with the two amide oxygen atoms. Two isomeric forms of the ?? has been isolated. The kinetic product obtained by combination of nickel(Ⅱ) salt with the free ligand was converted to the second isomer by heating in the appropriate solvent. Conductivity of [Ni(F)](ClO₄)₂in DMSO shows 2:1 electolyte.
Pendant functional group이 있는 macrocyclic tetraamine의 금속이온에 대한 선택성
고광오 순천향대학교 기초과학연구소 1997 순천향자연과학연구 논문집 Vol.3 No.2
Nickel(Ⅱ) complexes of the ligands 1,4,8,11-tetrakis(2-cyanoethyl)-1,4,8,12-tetraazacyclopentadecane(E) and 1,4,8,11-tetrakis(2-carbamoylethyl)-1,4,8,12-tetraazacyclopentadecane(F) were synthesized. Heating ?? in water resulted in formation of a complex of 1,8-bis(2-carbamoylethyl)-4-(2-cyanoethyl)-1,4,8,12-tetraazacyclopentadecane(G). [Ni(G)](ClO₄)₂shows it to contain a six-coordinate nickel ion with the two amide oxygen atoms. [Ni(F)](ClO₄)₂has octahedral geometry. Conductivity of [Ni(F)](ClO₄)₂in DMSO shows 2:1 electolyte.
Pendant CN group과 결합된 거대고리 tetraamine의 Ni(Ⅱ), Cu(Ⅱ) 착물의 구조
고광오 순천향대학교 기초과학연구소 1996 순천향자연과학연구 논문집 Vol.2 No.2
Structures of Ni(Ⅱ), Cu(Ⅱ) complexes with macrocyclic ligand(NN'N''N'''-tetra(2-cyanoethyl)-1,4,8,11-tetraazacyclotetradecane; L¹) were investigated using the spectroscopic method and conductivity measurement. Macrocyclic ligands were purified by recrystallization method(acetonitrile, ethanol, water solvents). Reaction of 1,4,8,11-tetraazacyclo-tetradecane with excess of acrylonitrile yields quantitatively the tetracyanoethylated product. In solid state, there is no interaction between Ni(Ⅱ), and the pendant CN in NiL¹Cl₂. For NiL¹Cl₂, two CN bands are seen. These peaks represent the presence of free and end on coordinated nitriles. In CuL¹(SCN)₂, there is no interaction between Cu(Ⅱ) and the nitrile group. In solution state of NiL¹Cl₂, in DMSO , the CI- ligand is exchanged by DMSO solvent. In CuL¹(NCS)₂the NCS- ligand is affected by DMSO. Conductivity of NiL¹Cl₂in DMF is more dependant on the concentration than that in DMSO.