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Article

Self-Assembled Copper(II) Coordination Polymers Derived from Aminopolyalcohols and Benzenepolycarboxylates: Structural and Magnetic Properties

Supporting Info

Alexander M. Kirillov,^† Yauhen Y. Karabach,^† Matti Haukka,^‡ M. Fátima C. Guedes da Silva,^†^§ Joaquin Sanchiz, Maximilian N. Kopylovich,^† and Armando J. L. Pombeiro*^†

Centro de Qumica Estrutural, Complexo I, Instituto Superior Tcnico, TU Lisbon, Av. Rovisco Pais, 1049-001, Lisbon, Portugal, University of Joensuu, Department of Chemistry, P.O. Box 111, FIN-80101, Joensuu, Finland, Universidade Lusfona de Humanidades e Tecnologias, Av. do Campo Grande, 376, 1749-024, Lisbon, Portugal, Departamento de Qumica Inorgnica, Universidad de La Laguna, 38200 La Laguna, Tenerife, Spain

Inorg. Chem., 2008, 47 (1), pp 162–175

DOI: 10.1021/ic701669x

Publication Date (Web): December 11, 2007

†

Instituto Superior Técnico.

‡

University of Joensuu.

Universidade Lusófona de Humanidades e Tecnologias.

Universidad de La Laguna.

To whom correspondence should be addressed. E-mail: pombeiro@ ist.utl.pt, Phone: +351 218419237, Fax: +351 218464455 (A.J.L.P.).

Abstract

The new copper(II) or copper(II)/sodium(I) 1D coordination polymers [Cu₂(Hmdea)₂(μ-H₂O)(μ₂-tpa)]_n·2nH₂O (1), [Cu₂(H₂tipa)₂(μ₂-ipa)]_n·4nH₂O (2), [Cu₂(H₂tea)₂Na(H₂O)₂(μ₂-tma)]_n·6nH₂O (3), [Cu₂(H₂tea)₂(μ₂-ipa)]_n·nH₂O (4a), and [Cu₂(H₂tea)₂{μ₃-Na(H₂O)₃}(μ₃-ipa)]_n(NO₃)_n·0.5nH₂O (4b) have been prepared in aqueous medium by self-assembly from copper(II) nitrate, aminopolyalcohols [methyldiethanolamine (H₂mdea), triisopropanolamine (H₃tipa), and triethanolamine (H₃tea)] as main chelating ligands and benzenepolycarboxylic acids [terephthalic (H₂tpa), isophthalic (H₂ipa), and trimesic (H₃tma) acid] as spacers. They have been characterized by IR spectroscopy, elemental and single-crystal X-ray diffraction analyses, the latter indicating the formation of unusual multinuclear metal cores interconnected by various benzenepolycarboxylate spacers, leading to distinct wavelike, zigzag, or linear 1D polymeric metal−organic chains. These are further extended to 2D or 3D hydrogen-bonded supramolecular networks via extensive interactions with the intercalated crystallization water molecules. The latter are associated, also with aqua ligands, by hydrogen bonds resulting in acyclic (H₂O)₃ clusters in 1, (H₂O)₈ clusters in 2, infinite 1D water chains in 3, and disordered water−nitrate associates in 4b, all playing a key role in the structure stabilization and its extension to further dimensions. Variable-temperature magnetic susceptibility measurements have shown that 1−4 exhibit a moderately strong ferromagnetic coupling through the alkoxo bridge. The small Cu−O−Cu bridging angle and the large out-of-plane displacement of the carbon atom of the alkoxo group accounts for this behavior. The magnetic data have been analyzed by means of a dinuclear and a 1D chain model, and the magnetic parameters have been determined. The magnetic exchange coupling in 3, to our knowledge, is the highest found in alkoxo-bridged copper(II) complexes.