Studies of the Copper(II) and Nickel(II) Complexes with Macrocyclic Ligands

Abstract

{[Ni(L)(4,4'-bpdc)]·3H₂O}_(n) (1), {[Ni(L)(2,6-ndc)]·2MeCN}_(n) (2) {[Ni(L1)(tp)]·6H₂O}_(n) (3), {[Cu₃(L1)₂(4,4'-bpdc)(H₂O)₄]·(4,4'-bpdc)₂·(H₂O)_(18)}_(n) (4) and [Cu(L1)(H₂O)₂](2,6-ndc) (5) (L = 1,8-hydroxylethyl-1,3,6,8,10,13-hexaazacyclotetradecane, L1 = 1,8-di(1-propyl-imidazole)-1,3,6,8,10,13-hexaazacyclotetradecane, tp = terephthalic acid dianion, 4,4'-bpdc = 4,4'-biphenyldicarboxylic acid dianion, 2,6-ndc = 2,6-naphthalenedicarboxylic acid dianion) 의 조성을 갖는 5개의 구리(II)와 니켈(II) 화합물을 합성하였고, 분석, 분광학 및 X-ray 결정학적 방법을 통해 구조적인 특징을 알아 낼 수 있었다. 일부 착화합물의 경우, 각각의 금속 이온을 polycarboxylate 음이온이 다리연결을 함으로써 1차원 배위고분자를 형성하였다. 특히 4번째 화합물의 구조에서는 [Cu(L1)](ClO₄)₂ 와 4,4'-biphenyldicarboxylic acid 가 결합함으로써 2차원 배위고분자가 만들어졌다. 모든 착화합물에서는 다양한 형태의 수소결합 상호작용이 구조적인 기하구조를 결정하는데 중요한 역할을 한다.

Five new nickel(II) and copper(II) complexes with the composition {[Ni(L)(4,4'-bpdc)]·3H₂O}_(n) (1), {[Ni(L)(2,6-ndc)]·2MeCN}_(n) (2) {[Ni(L1)(tp)]·6H₂O}_(n) (3), {[Cu₃(L1)₂(4,4'-bpdc)(H₂O)₄]·(4,4'-bpdc)₂·(H₂O)_(18)}_(n) (4) and [Cu(L1)(H₂O)₂](2,6-ndc) (5) (L = 1,8-dihydroxylethyl-1,3,6,8,10,13-hexaazacyclotetradecane, L1 = 1,8-di(1-propyl-imidazole)-1,3,6,8,10,13-hexaazacyclotetradecane, tp = terephthalic acid dianion, 4,4'-bpdc = 4,4'-biphenyldicarboxylic acid dianion, 2,6-ndc = 2,6-naphthalenedicarboxylic acid dianion) have been synthesized and structurally characterized by a combination of analytical, spectroscopic, and X-ray crystallography. Some complexes show one-dimensional coordination polymers in which each metal ion is bridged by polycarboxylate ions. Specially, in the structure of 4, 2D coordination polymer is formed by the reaction between [Cu(L1)](ClO₄)₂ and 4,4'-biphenyldicarboxylic acid. In all complexes, various types of hydrogen bonding interactions play an important role in determining the shapes of structural geometries.