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Issue 8, 2008
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Synthesis and structural characterisation of lanthanide coordination polymers featuring 4,4′,6,6′-tetra-carboxy-2,2′-bipyridine and rare network topology

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Abstract

Reported herein is a synthetic and structural study of the coordination chemistry of 4,4′,6,6′-tetracarboxylic acid-2,2′-bipyridine (H4tcbp) with some lanthanide ions. The reaction of H4tcbp under acidic hydrothermal conditions with Ln(III) (Ln = La, Eu and Gd) in 1 : 1 stoichiometric ratio led to the formation of crystalline {[La(Htcbp)(H2O)3]·H2O}, 1, {[La(Htcbp)(H2O)]}, 2, {[Eu(Htcbp)(H2O)]·2 H2O}, 3 and {[Gd(Htcbp)(H2O)]·2 H2O}, 4; which were structurally characterised. Using a 1 : 1 H2O/DMF-solution in combination with Eu(III) and H4tcbp gave {[Eu(tcbp)(H2O)]·(Me2NH2)}, 5, which was also structurally characterised. The acidic conditions in 14 yielded 1 : 1 neutral {Ln : Htcbp} complexes whereas in 5 the H4tcbp ligand is fully deprotonated and charge neutrality is brought about by the presence of a dimethylammonium cation (arising through the hydrolysis of the DMF solvent). Complex 1 forms a 1D coordination polymer which cross-links through extensive hydrogen bonding to form a complicated 3D network. Each {Ln(Htcbp)} moiety in 2 acts as a four-connecting node and forms a 2D sheet with (4,4)-topology, which is different to the 2D sheets with (4,4)-topology formed in isostructural 3 and 4. Within 5 each [Eu(tcbp)] moiety acts as a 5-connecting node forming a heretofore unprecedented 2D 5-connected network with (33.43.54) topology. Furthermore, each 2D sheet in 25 features an array of hydrogen bonded contacts both within and between neighbouring sheets to give complicated 3D networks.

Graphical abstract: Synthesis and structural characterisation of lanthanide coordination polymers featuring 4,4′,6,6′-tetra-carboxy-2,2′-bipyridine and rare network topology

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Publication details

The article was received on 04 Feb 2008, accepted on 08 Apr 2008 and first published on 09 May 2008


Article type: Paper
DOI: 10.1039/B801985A
CrystEngComm, 2008,10, 1018-1026

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    Synthesis and structural characterisation of lanthanide coordination polymers featuring 4,4′,6,6′-tetra-carboxy-2,2′-bipyridine and rare network topology

    N. R. Kelly, S. Goetz, S. R. Batten and P. E. Kruger, CrystEngComm, 2008, 10, 1018
    DOI: 10.1039/B801985A

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