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Issue 47, 2008
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Curly–curly, loop–loop: homoleptic metal(ii) complexes of pyridinecarbaldehyde 4′-(2,2′:6′,2″-terpyridyl)hydrazones and their coordination polymers

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Abstract

The ligands 4-, 3- and 2-pyridinecarbaldehyde 4′-(2,2′:6′,2″-terpyridyl)hydrazone (1, 2 and 3) have been prepared and characterized. In the homoleptic iron(II) and ruthenium(II) complexes, the nitrogen donor atoms of the pendant pyridine rings subtend an obtuse angle (≈155°) at the metal centre, thus providing an expanded ligand, which can be used for the assembly one-dimensional coordination polymers with an undulating backbone. Protonation of the pendant pyridine rings in [FeL2]2+ (L = 1, 2, 3) or [RuL2]2+ (L = 1, 2) leads to a colour change from purple to blue, or red to pink, respectively, as the MLCT band shifts to a lower energy. The structural data for [Fe(H2)(2)][PF6]3·3.5MeCN·2.5H2O (where [H2]+ is the monoprotonated ligand) show that the [Fe(H2)(2)]3+ cations form one-dimensional chains supported by NpyH⋯Npy hydrogen bonds and that the undulating chains pack to give a porous material, with channels that accommodate the anions and solvent molecules. A single-crystal X-ray diffraction determination of {[Fe(NCS)2(Ru(1)2)2][Fe2(NCS)6(OEt)2(EtOH)2][NCS]2·4EtOH·H2O}n reveals that pairs of [Ru(1)2]2+ cations connect {Fe(NCS)2} units to give a one-dimensional polymer comprising of linked metallamacrocycles.

Graphical abstract: Curly–curly, loop–loop: homoleptic metal(ii) complexes of pyridinecarbaldehyde 4′-(2,2′:6′,2″-terpyridyl)hydrazones and their coordination polymers

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Supplementary files

Article information


Submitted
26 Jun 2008
Accepted
15 Aug 2008
First published
16 Oct 2008

Dalton Trans., 2008, 6742-6751
Article type
Paper

Curly–curly, loop–loop: homoleptic metal(II) complexes of pyridinecarbaldehyde 4′-(2,2′:6′,2″-terpyridyl)hydrazones and their coordination polymers

J. E. Beves, E. C. Constable, C. E. Housecroft, C. J. Kepert, M. Neuburger, D. J. Price, S. Schaffner and J. A. Zampese, Dalton Trans., 2008, 6742
DOI: 10.1039/B810906K

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