Abstract
Two types of Pd-complexes containing the new N, N′-ligands 2-[3-(4-alkyloxyphenyl)pyrazol-1-yl]pyridine (pz Rpy; R = C 6H 4OC n H 2 n+1 , n = 6 (hp), 10 (dp), 12 (ddp), 14 (tdp), 16 (hdp), 18 (odp)) ( 1– 6), namely c-[Pd(Cl) 2(pz Rpy)] ( 7– 10) and c-[Pd(η 3-C 3H 5)(pz Rpy)]BF 4 ( 11– 16), have been synthesised and characterised by different spectroscopic techniques. Those members of the second type containing the largest chains (R = ddp 13, tdp 14, hdp 15, odp 16) have been found to have liquid crystal properties showing smectic A mesophases. By contrast, neither the free ligands pz Rpy nor their related c-[Pd(Cl) 2(pz Rpy)] complexes exhibited mesomorphism. The new synthesised metallomesogens are mononuclear complexes with an unsymmetrical molecular shape as deduced from the X-ray structures of c-[Pd(η 3-C 3H 5)(pz Rpy)]BF 4 (R = hp, 11; dp, 12). Both compounds, which are isostructural, show a distorted square-planar environment on the palladium centres defined by the allyl and the bidentate pz Rpy ligands. The crystal structure reveals that both the counteranion and the pz Rpy ligand function as a source of hydrogen-bonding and intermolecular π⋯π contacts resulting in a 2D supramolecular assembly.
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