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Issue 25, 2006
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Extended three-dimensional supramolecular architectures derived from trinuclear (bis-β-diketonato)copper(II) metallocycles

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Abstract

Neutral trinuclear (triangular) copper(II) complexes of type [Cu3L3] incorporating the 1,4-aryl linked bis-β-diketonato bridging ligands, 1,1-(1,4-phenylene)-bis(butane-1,3-dione) (H2L2), 1,1-(1,4-phenylene)-bis(pentane-1,3-dione) (H2L3) and 1,1-(1,4-phenylene)-bis(4,4-dimethylpentane-1,3-dione) (H2L4) have been demonstrated to react with selected heterocyclic nitrogen donor bases to generate extended supramolecular architectures whose structures have been confirmed by X-ray diffraction. Thus on reaction with 4,4′-bipyridine (bipy), [Cu3(L2)3] yields polymeric structures of type {[Cu3(L2)3(bipy)(THF)]·2.75THF}n and {[Cu3(L2)3(bipy)(THF)]·bipy·0.75THF}n while with pyrazine (pyz), {[Cu3(L2)3(pyz)]·0.5THF}n was obtained. Each of these extended structures contain alternating triangle/linker units in a one-dimensional polymeric chain arrangement in which two of the three copper sites in each triangular ‘platform’ are formally five-coordinate through binding to a heterocyclic nitrogen atom. Interaction of the multifunctional linker unit hexamethylenetetramine (hmt) with [Cu3(L3)3] afforded an unusual, chiral, three-dimensional molecular framework of stoichiometry [Cu3(L3)3(hmt)]n. The latter incorporates the trinuclear units coordinated to three triply bridging hmt units. In marked contrast to the formation of the above structures incorporating bifunctional linker units and five-coordinate metal centres, the trinuclear platform [Cu3(L2)3] reacts with the stronger difunctional base 1,4-diazabicyclo[2.2.2]-octane (dabco) to yield a highly symmetric trigonal columnar species of type {[Cu3(L4)3(dabco)3]·3H2O}n in which each copper centre is octahedrally coordinated.

Graphical abstract: Extended three-dimensional supramolecular architectures derived from trinuclear (bis-β-diketonato)copper(ii) metallocycles

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Publication details

The article was received on 06 Dec 2005, accepted on 27 Feb 2006 and first published on 15 Mar 2006


Article type: Paper
DOI: 10.1039/B517274H
Citation: Dalton Trans., 2006,0, 3114-3121
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    Extended three-dimensional supramolecular architectures derived from trinuclear (bis-β-diketonato)copper(II) metallocycles

    J. K. Clegg, L. F. Lindoy, J. C. McMurtrie and D. Schilter, Dalton Trans., 2006, 0, 3114
    DOI: 10.1039/B517274H

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