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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 33, Number 8
BKCSDE 33(8)
August 20, 2012 

 
Title
One-Pot Reaction Involving Two Different Amines and Formaldehyde Leading to the Formation of Poly(Macrocyclic) Cu(II) Complexes
Author
Yun-Taek Lee, Shin-Geol Kang*
Keywords
Polynuclear complex, Poly(macrocyclic) complex, Polymer complex, Copper(II) complex, Functional pendant arm
Abstract
New polynuclear poly(hexaaza macrocyclic) copper(II) complexes [1](ClO4)2n·(H2O)2n, [2](ClO4)2n·(H2O)2n, and [3](ClO4)2n·(H2O)2n have been prepared by the one-pot reaction of formaldehyde with ethylenediamine and 1,2-bis(2-aminoethoxy)ethane, 1,3-diaminopropane, or 1,6-diaminohexane in the presence of the metal ion. The polymer complexes contain fully saturated 14-membered hexaaza macrocyclic units (1,3,6,8,10,13-hexaazacyclotetradecane) that are linked by N-(CH2)2-O-(CH2)2-O-(CH2)2-N, N-(CH2)3-N, or N-(CH2)6-N chains. The mononuclear complex [Cu(H2L5)](ClO4)4 (H2L5 = a protonated form of L5) bearing two N-(CH2)2-O- (CH2)2-O-(CH2)2-NH2 pendant arms has also been prepared by the metal-directed reaction of ethylenediamine, 1,2-bis(2-aminoethoxy)ethane, and formaldehyde. The polymer complexes were characterized employing elemental analyses, FT-IR and electronic absorption spectra, molar conductance, X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and scanning electron micrograph (SEM). Electronic absorption spectra of the complexes show that each macrocyclic unit of them has squareplanar coordination geometry with a 5-6-5-6 chelate ring sequence. The polymer complexes as well as [Cu(H2L5)]4+ are quite stable even in concentrated HClO4 solutions. Synthesis and characterization of the polynuclear and mononuclear copper(II) complexes are reported.
Page
2517 - 2522
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