Towards inert and preorganized d-block-containing receptors for trivalent lanthanides: the synthesis and characterization of triple-helical monometallic Os(II) and bimetallic Os(II)-Ln(III) complexes

The mononuclear Os(II) complex [Os()(3)](PF(6))(2) ( = 5-methyl(1-methylbenzimidazol-2-yl)pyridine) is an obvious candidate for the design of an inert d-block-based tripodal receptor capable of binding and photosensitizing trivalent lanthanides (Ln(III)). It has thus been prepared and its two enantiomeric meridional (Delta-mer and Lambda-mer) and facial (rac-fac) isomers have been separated by ion-exchange chromatography. The optical isomers have been characterized by CD spectroscopy and assignments of absolute configuration confirmed by an X-ray crystallographic study of Lambda-mer-[Os()(3)](PF(6))(2).1.5MeCN (monoclinic, P2(1), Z = 4). Comparison of the latter structure with that of racemic fac-[Os()(3)](PF(6))(2) (monoclinic, C2/c, Z = 8) and [Os(bipy)(3)](PF(6))(2) (where bipy = 2,2'-bipyridine) shows minimal structural variations, but differences are observed in the photophysical and electrochemical properties of the respective compounds. Luminescence emissions from Os(II) complexes of are typically lower in energy, with shorter lifetimes and lower quantum yields than their bipy analogues, whilst metal-centred oxidation processes are more facile due to the enhanced pi-donor ability of . The key relationships between these parameters are discussed. Finally, though challenged by (i) the low reactivity of many osmium precursors and (ii) the irreversible formation of competing side products, the synthesis and purification of the heterobimetallic triple-stranded helicate HHH-[OsLu()(3)](CF(3)SO(3))(5) has been realised, in which is a segmental ligand containing the same bidentate unit as that found in further connected to a tridentate binding site adapted for complexing Ln(III). Its solid-state structure has been established by X-ray crystallography (triclinic, P1, Z = 2).