(Ln([20]DOTA)(NO₃)(H₂O)]²+(Ln=Pr³+, Sm³+, Gd³+, Dy³+) 착이온과 두자리 보조리간드(주게원자 ; N 혹은 O) 간의 화학평형 = Chemical Equilibria of (Ln([20]DOTA)(NO₃)(H₂O)]²+(Ln=Pr³+, Sm³+, Gd³+, Dy³+) Complex Ions with N- or O-Containing Bidentate Auxiliary Ligands.

국문 초록 (Abstract)

2-hydroxy-3-hydroxymethyl-5-methylbenzaldehyde(HHMMB)와 ethylenediamine 혹은 1, 3- diaminopropane의 축합반응에 의해 6-배위 칸막이 리간드 H₄L[A]와 H₄L[B]를 각각 얻은 후에 거대비고리 리간드 착물, Cu(H₂L[A])·H₂O, Cu(H₂L[B])·H₂O, CuFe(L[A])(NO₃)·4H₂O, CuFe(L[B])(NO₃)·4H₂O, [CuGd(H₂L[A])(NO₃)₂](NO₃)·2CH₃OH, [CuGd(H₂L[B])(NO₃)₂](NO₃)·2CH₃OH를 합성하였다. 2, 6-diformyl-p-cresol(DFPC)로부터 합성한 Ln-거대고리([20]DOTA)착물, [Ln([20]DOTA)(NO₃)(H₂O)](NO₃)·χH₂O{Ln(Ⅲ)=Pr, Sm, Gd, Dy}를 methanol용매에 2일 정도 정치함으로써 [Ln([20]DOTA)(NO₃)(CH₃OH]²+ 을 얻을 수 있다. 이 lanthanide[20]DOTA착물에서 배위된 CH₃OH이 주게원자가 N 혹은 O인 두자리 보조리간드, La(=0-phenylenediamine, 1, 10-phenanthroline, ethylenediamine, oxalic acid, malonic acid, acethylaceton)에 의해 치환될 때 평형상수(K)를 25℃ μ=0.1M NaClO₄에서 분광학적 방법으로 결정하였다. 보조리간드의 pKa는 o-phenylenediamine <1, 10-phenanthroline < ethylenediamine, oaxlic acid < malonic acid < acethylacetone이며, 이때 평형상수, K는 ethylenediamine < 1, 10-phenanthroline < o-phenylenediamine, acethylacetone < malonic acid < oxalic acid 경향으로 변하였다.

다국어 초록 (Multilingual Abstract)

Macroacyclic transition metal complexes such as Cu(H₂L[A])·H₂O, Cu(H₂L[B])·H₂O, CuFe(L[A])(NO₃)·4H₂O, CuFe(L[B])(NO₃)·4H₂O,[CuGd(H₂L[A])(NO₃)₂](NO₃)·2CH₃OH,[CuGd(H₂L[B])(NO₃)₂](NO₃)·2CH₃OH were prepared from the correponding hexadentate compartmental ligands, H₄L[A] and H₄L[B], which were obtained by the condensation of 2-hydroxy-3-hydroxymethyl-5-methylbenzaldehyde (HHMMB) and ethylenediamine or 1, 3-diaminopropane. Ln-macrocyclic([20]DOTA) complex, [Ln([20]DOTA)(NO₃)(H₂O)] (NO₃)₂·χH₂O{Ln(Ⅲ)=Pr, Sm, Gd, Dy}, which had been synthesized from 2, 6-diformyl-p-cresol(DFPC), was placed in methanol for 2 days, and (Ln([20]DOTA)(NO₃)(CH₃OH)]²+ was formed. The equilibrium constants (K) for the substitution of coordinated CH₃OH in the Ln-[20]DOTA complexes by various bidentate auxiliary ligands, La(=0-phenylenediamine, 1,10-phenanthroline, ethylenediamine, oxalic acid, malonic acid, acethylacetone) were determined by spectroscopic method at 25℃ and 0.1M NaClO₄. The pKa of auxiliary ligands is in the order of o-phenylenediamine < 1, 10-phenanthroline < ethylenediamine, oaxlic acid < malonic acid < acethylacetone, however the equilibrium constant(K) has shown the trend of ethylenediamine < 1, 10-phenanthroline < ethylenediamine oxalic and < malonic acid < acethylacetone, however the equilibrium costant(K) has shown the trend of ethylenediamine < 1, 10-phenanthroline < o-phenlenediamine, acethylacetone < malonic acid < oxalic acid.