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Syntheses, isolation, and structures of nickel(II) and copper(II) coordination polymers with a tetraaza macrocyclic ligand

✍ Scribed by Ju Chang Kim; Jaeheung Cho; Alan J Lough


Publisher
Elsevier Science
Year
2001
Tongue
English
Weight
152 KB
Volume
317
Category
Article
ISSN
0020-1693

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✦ Synopsis


The one-dimensional coordination polymers [Ni(L1)(oxalato)] n β€’nH 2 O (1) and [Cu(L1)(terephthalato)] n β€’2nH 2 O (2) have been synthesized and structurally characterized by a combination of analytical, spectroscopic, and crystallographic methods. The complex 1 exhibits a novel one-dimensional polymeric structure with nickel(II) centers and bridging oxalato ligands. Two important features are observed in 1 when regarding the structure of the oxalato bridge: first, it has an unusual bis-monodentate coordination mode to nickel(II) ions; and second, it is not planar, the distortion arising forms a twisting about the carbon-carbon bond of the oxalato ligand. In 2, the ligand conformation is planar, and the distorted octahedral coordination about the copper(II) ion is completed by two bis-monodentate terephthalato ligands. The copper(II) ions in the complex are bridged by the terephthalato anions to form infinite linear chains, and each chain is linked by interchain hydrogen bonding interactions mediated through water molecules. The presence of water molecules is crucial to lead supramolecular arrays in both complexes.


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Electronic structures of square planar c
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ESR and absorption spectra were measured for the square planar cobalt(II), nickel(II) and copper complexes with some I4, 15 and 16membered N4macrocyclic ligands, such as (14-a), H(14-b), H,(14c), HJIS-c) and H,(16-c) (for the abbreviations, see Fig. 2 in the text). On the basis of the ESR spectra of