Homochiral Carboxylate-Anchored Truxene Tripods: Design, Synthesis, and Monolayer Formation on Ag(111)

The design of well-defined assemblies of chiral molecules is a prerequisite for numerous applications, such as chirality-induced spin selectivity (CISS). In this context, tripodal molecular films bear the advantage of better control of molecular orientation and alignment than analogous monopodal systems. To this end, we report on the synthesis and assembly property of C₃ chiral syn-5,10,15-truxene triacetic acid. (S,S,S) and (R,R,R) enantiomers were isolated and adsorbed on underpotential deposited Ag(111)/Au/mica both individually and as a racemate. The enantiomers form a densely packed and well-ordered structure (including the azimuthal alignment), even though with small sizes of individual domains. The molecules adsorb predominantly in tripodal configuration, with all three docking groups bound to the substrate as carboxylates in a bidentate fashion. The truxene backbone is then oriented parallel to the substrate surface but the fluorene blades are twisted to some extent. The racemate monolayer turned out to be less densely packed and less well-ordered compared to the films of individual enantiomers, which underlines the fact that uniform chirality is primarily important for molecular ordering of the truxenes. We hope that the designed system will be useful in the context of CISS and stimulate further activities regarding chiral tripods.