Star‐Shaped Ruthenium Complexes as Prototypes of Molecular Gears
Résumé
The design and synthesis of two families of molecular gears prototypes is reported, with the aim of assembling them into trains of gears on surface and ultimately achieving controlled intermolecular gearing motion. These piano-stool ruthenium complexes incorporate a hydrotris(indazolyl)borate moiety as tripodal rotation axle and a pentaarylcyclopentadienyl ligand as star-shaped cogwheel, equipped with five teeth ranging from pseudo 1-dimensional aryl groups to large planar 2-dimensional paddles. A divergent synthetic approach was followed, starting from a penta(p-bromophenyl)cyclopentadienyl ruthenium(II) complex as key precursor or from its iodinated counterpart, first obtained by copper-catalyzed aromatic Br/I exchange. Subsequent five-fold cross-coupling reactions with various partners allowed high structural diversity to be reached, yielding molecular gears prototypes displaying aryl-, carbazole-, BODIPY-and porphyrin-derived teeth of increasing size and length.
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