Journal
DALTON TRANSACTIONS
Volume -, Issue 44, Pages 5140-5147Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/b711655a
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- ICREA Funding Source: Custom
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The reaction in water of Cu(OH)(2) with 2,2'-bipyridine (bipy) and (NH4)(2)HPO4 in a 4 : 4 : 2 molar ratio under an inert atmosphere leads to the formation of a tetranuclear copper(II) complex of formula {[(H2O)(2)Cu-4(bipy)(4)(mu(4)-PO4)(2)(mu(2)-OH)]center dot 0.5HPO(4)center dot 15.5H(2)O}, 1, with butterfly topology. The structure of the tetranuclear core in 1 consists of four crystallographically unique copper(II) ions in approximate square-pyramidal geometry with each coordinated to a bipy ligand and interacting through two mu(4)-O,O',O-phosphate bridges. Additional bridging between Cu(3) and Cu(4) is provided by a hydroxide ligand, whereas two water molecules cap the Cu(1) and Cu(2) square pyramids to yield a N2O3 chromophore at each copper atom. Adjacent tetranuclear units align in anti-parallel fashion where proximate metal-bound water molecules interact with each other through both intra- and inter-molecular H-bonding to link two such clusters. These pairs then further associate through pi center dot center dot center dot pi interactions between bipy ligands to form a 2D sheet with neighbouring sheets separated by H-bonded lattice water molecules, which form a 2D H-bonded network. Variable-temperature magnetic susceptibility measurements performed upon 1 reveal net intramolecular ferromagnetic coupling between the copper(II) ions and this is supported and rationalized by a DFT study.
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