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Updated: Feb 16, 2026

Microscopic Visualization of Porous Nanographenes Synthesized through a Combination of Solution and On-Surface Chemistry
Published on: March 4, 2021
Superphenylphosphines: Nanographene-Based Ligands That Control Coordination Geometry and Drive Supramolecular
Jordan N Smith1, James M Hook2, Nigel T Lucas1
1MacDiarmid Institute for Advanced Materials and Nanotechnology, Department of Chemistry, University of Otago , Union Place, Dunedin 9016, New Zealand.
Abstract:
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.
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