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

Citations Over TimeTop 10% of 2007 papers

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.

Related Papers

• → The co-crystallisation of pyridine with benzenepolycarboxylic acids: The interplay of strong and weak hydrogen bonding motifs(2004)102 cited
• → Solvothermal synthesis, structure and properties of a new 3-D Cu(I)–Gd(III) heterometallic coordination framework(2011)7 cited
• → Adsorptive and Photocatalytic Dye Removal from Wastewater Using Metal-Organic Frameworks(2020)2 cited
• → X-ray crystallographic study of hydrogen-bonded systems formed between di- and tricarboxylic acids and the trinuclear cluster cation [H3Ru3(C6H6)(C6Me6)2(O)]+(2005)5 cited
• Analysis of acetic acid by-product in the polymerization reaction of hydroquinone diacetate, acetoxybenzoic acid, trimesic acid, and isophthalic acid and testing of a new polymer in the application of the bonding material in grinding wheels(1996)