Issue 44, 2007
From the journal:

Dalton Transactions

Metamorphosis of a butterfly: synthesis, structural, thermal, magnetic and DFT characterisation of a ferromagnetically coupled tetranuclear copper(ii) complex†‡§

Robert P. Doyle,*a   Thomas Bauer,a   Miguel Julve,*b   Francesc Lloret,b   Joan Cano,c   Mark Nieuwenhuyzend  and  Paul E. Kruger*e  

* Corresponding authors

a Department of Chemistry, Syracuse University, Syracuse, New York, USA
E-mail: rpdoyle@syr.edu

b Department of Química Inorgànica/Instituto de Ciencia Molecular, Universitat de València, Polígono La Coma s/n, E-46980 Paterna, Valencia, Spain
E-mail: miguel.julve@uv.es

c Institució Catalana de Recerca i Estudis Avançats (ICREA), Departament de Química Inorgànica, Institut de Química Teòrica i Computacional (IQTC) and Institut de Nanociència i Nanotecnologia (IN2UB), Universitat de Barcelona, Barcelona, Spain

d Department of Chemistry, Queen's University, Belfast, BT9 5AG, UK

e Department of Chemistry, College of Science, University of Canterbury, Christchurch, New Zealand
E-mail: paul.kruger@canterbury.ac.nz

Abstract

The reaction in water of Cu(OH)2 with 2,2′-bipyridine (bipy) and (NH4)2HPO4 in a 4 : 4 : 2 molar ratio under an inert atmosphere leads to the formation of a tetranuclear copper(II) complex of formula {[(H2O)2Cu4(bipy)4(μ4–PO4)2(μ2–OH)]·0.5HPO4·15.5H2O}, 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 μ4–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 π⋯π 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.

Graphical abstract: Metamorphosis of a butterfly: synthesis, structural, thermal, magnetic and DFT characterisation of a ferromagnetically coupled tetranuclear copper(ii) complex

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Article information

DOI
https://doi.org/10.1039/B711655A
Article type
Paper
Submitted
30 Jul 2007
Accepted
17 Sep 2007
First published
28 Sep 2007

Dalton Trans., 2007, 5140-5147

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Metamorphosis of a butterfly: synthesis, structural, thermal, magnetic and DFT characterisation of a ferromagnetically coupled tetranuclear copper(II) complex

R. P. Doyle, T. Bauer, M. Julve, F. Lloret, J. Cano, M. Nieuwenhuyzen and P. E. Kruger, Dalton Trans., 2007, 5140 DOI: 10.1039/B711655A

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