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| Azevedo, Nuno Monteiro |
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Williams, Bailey R.
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article
Polynuclear and coordination polymers of copper(II) complexes assembled by flexible polyamines and bridging rigid N-heterocyclic multicarboxylates
Abstract
<p>Four trinuclear Cu(II) complexes bridged by N-heterocyclic multicarboxylic acids: [Cu<sub>3</sub>(dien)<sub>2</sub>(μ<sub>2</sub>-Pz<sup>3,5-dc</sup>)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]·4H<sub>2</sub>O (1), [Cu<sub>3</sub>(pmdien)<sub>2</sub>(μ<sub>2</sub>-Py<sup>2,5-dc</sup>)<sub>2</sub>(ClO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (2), [Cu<sub>3</sub>(trpn)<sub>2</sub>(μ<sub>2</sub>-Py<sup>2,5-dc</sup>)<sub>2</sub>(ClO<sub>4</sub>)<sub>2</sub>] (3) and [Cu<sub>3</sub>(ip<sub>3</sub>tren)<sub>2</sub>(μ<sub>2</sub>-Py<sup>2,4-dc</sup>)<sub>2</sub>(H<sub>2</sub>O)](ClO<sub>4</sub>)<sub>2</sub> (4) and the coordination polymer: catena-[Cu<sub>2</sub>(bedmpza)<sub>2</sub>(μ<sub>2</sub>-Py<sup>2,4-dc</sup>)](ClO<sub>4</sub>)<sub>2</sub>·H<sub>2</sub>O (5) as well as the monomeric [Cu(bdmpzpy)(Py<sup>2,6-dc</sup>)]<sub>2</sub>·3H<sub>2</sub>O (6), where H<sub>3</sub>Pz<sup>3,5-dc</sup> = 3,5-pyrazole dicarboxylic acid, H<sub>2</sub>Py<sup>2,4-dc</sup> = 2,4-pyridine dicarboxylic acid, H<sub>2</sub>Py<sup>2,5-dc</sup> = 2,5-pyridine dicarboxylic acid, H<sub>2</sub>Py<sup>2,6-dc</sup> = 2,6-pyridine dicarboxylic, dien = diethylenetriamine, pmedien = N,N,N′,N″,N″-pentamethyldiethylene-triamine, bedmpza = bis(3,5-dimethylpyrazolyl-1H-ethyl)amine, trpn = tris(3-aminopropyl)amine, ip<sub>3</sub>tren = tris(2-isopropyl-2-ethyl)amine and bdmpzpy = 2,6-bis[(3,5-dimethyl-1H-pyrazolyl)methyl]pyridine were synthesized. The compounds were structurally characterized by elemental microanalyses, IR and UV–Vis spectra as well as by single crystal X-ray crystallography for 1–3, 5 and 6. In 1–3 and 5, the N-heterocyclic multicarboxylate dianion linkers are simultaneously bound by at least one N,O chelating hetero-aromatic dicarboxylato anions via ring-N atom and one O-atom of the adjacent carboxylato group and an O-atom of the carboxylates located at the other side of the heteroxyclic ring. In complex 6 the adjacent bdmpzpy ligands constitute π-π interactions through the central pyridine rings with separation of the centers of gravities = 3.666(2) Å. The degree of nuclearity in the polynuclear species depends entirely on the skeletal structure of the linker N-heterocyclic multicarboxylic acids and the amine coligands.</p>