Superphenylphosphines: Nanographene-Based Ligands That Control Coordination Geometry and Drive Supramolecular Assembly

Tertiary phosphines remain widely utilized in synthesis, most notably as supporting ligands in metal complexes. A series of triarylphosphines bearing one to three hexa-peri-hexabenzocoronene (HBC) substituents has been prepared by an efficient divergent route. These “superphenylphosphines”, P­{HBC­(t-Bu)5}nPh3‑n (n = 1–3), form the palladium complexes PdCl2L2 and Pd2Cl4L2 where the isomer distribution in solution is dependent on the number of HBC substituents. The crystalline structures of five complexes all show intramolecular π-stacking between HBC-phosphines to form a supramolecular bidentate-like ligand that distorts the metal coordination geometry. When n = 2 or 3, the additional HBC substituents engage in intermolecular π-stacking to assemble the complexes into continuous ribbons or sheets. The phosphines adopt HBC’s characteristics including strong optical absorption, green emission, and redox activity.