Abstract
The synthesis and crystal structures of three new metal organic frameworks of type [Zn(L-2H)] n (1), {[ZnLCl2](CH3CN)0.5(DMF)0.5(H2O)0.5} n (2) and {[CdL(DMF)(NO3)2]·DMF} n (3), all based on the dipyridyl-derivatised macrocycle, dipyridyldibenzotetraaza[14]annulene (L), are reported along with the X-ray structure of the protonated metal-free ligand as its perchlorate salt, [(HL)(ClO4)] n (4). In [Zn(L-2H)] n , the zinc ion occupies the macrocyclic cavity, being bound to the N4-donor set of the macrocyclic ring in its doubly deprotonated form. Each zinc atom is also axially bound by a pyridyl moiety from an adjacent complex, resulting in formation of an infinite one-dimensional chain of the ‘herringbone’ type in which pairs of macrocyclic complexes interact via face-to-face π–π stacking interactions. In contrast, the zinc ion in {[ZnLCl2](CH3CN)0.5(DMF)0.5(H2O)0.5} n does not occupy the macrocyclic cavity but is bound to a pyridyl nitrogen from two ligands such that it acts as a bridge between macrocyclic units and results in the generation of a one-dimensional chain. Two chloro ligands also bind to each zinc centre to yield a distorted tetrahedral coordination geometry. Offset π–π stacking occurs between adjacent chains involving alternate macrocycles in each chain, giving rise to a zig-zag arrangement. Pairs of interacting chains pass through the above-mentioned chains to generate further π–π stacking to yield an overall three-dimensional structure that contains large ellipsoidal-shaped channels. In {[CdL(DMF)(NO3)2]·DMF} n the cadmium ion again does not occupy the macrocyclic cavity but acts as a bridge between macrocycles to once again afford a linear chain structure. Each cadmium is bound to two pyridyl groups (arising from different molecules of L), two nitrato ligands and one oxygen-bound dimethylformamide molecule to yield a distorted pentagonal bipyramidal coordination geometry. The protonated ligand, [(HL)(ClO4)] n , adopts a linear chain structure in which one pyridyl group is protonated and interacts intermolecularly via a hydrogen bond with the non-protonated pyridyl group of an adjacent macrocyclic unit to yield a hydrogen-bonded linear chain structure.
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We thank the Australian Research Council for support.
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Andrew Parkin—deceased.
Y. Mulyana, C. J. Kepert, J. McMurtrie, P. Turner, G. Wei and J. G. Wilson dedicate this manuscript to Prof. Len Lindoy in celebration of his 75th birthday.
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Mulyana, Y., Lindoy, L.F., Kepert, C.J. et al. New metal organic frameworks incorporating the ditopic macrocyclic ligand dipyridyldibenzotetraaza[14]annulene. J Incl Phenom Macrocycl Chem 71, 455–462 (2011). https://doi.org/10.1007/s10847-011-0007-6
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DOI: https://doi.org/10.1007/s10847-011-0007-6