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Two new N-heterocyclic carbene (NHC) ligands bearing 2-morpholino and 2-piperidinyl naphthyl wingtips were synthesised (2-SIMorNap and 2-SIPipNap). Nuclear magnetic resonance studies, in conjunction with crystal structures and derivatisation of the NHC salts using a chiral counteranion, revealed that the ligand wingtips are oriented anti with respect to each other. From the free carbene, palladium, ruthenium and iridium complexes were prepared. NHC–iridium dicarbonyl complexes were made in order to extract the TEP values for these ligands. The study showed that these NHC ligands are more electron-donating than normal, aryl-substituted NHCs. The palladium complexes were tested in representative Suzuki–Miyaura cross-coupling reactions and compared to the state of the art systems. Ruthenium-catalysed ring-closing metathesis with these ligands was also performed. It was found that Grubbs’ 2nd generation catalyst incorporating 2-SIPipNap did not initiate at room temperature and required heating for RCM to occur.

By combining 60° bis(ferrocenyl) di-Pt(II) acceptors and the complementary 120° dipyridyl or dicarboxylate donors substituted with [G-1]–[G-3] Frechet-type dendrons, self-assembly of a new series of charged or neutral dendritic tetrakis(ferrocenyl) rhomboids was realized under mild conditions in high yields, respectively. The structures of all difunctionalized rhomboids were characterized by multinuclear NMR (1H and 31P), ESI-TOF-MS, CSI-TOF-MS, and elemental analysis. Moreover, their electrochemical behavior was studied through cyclic voltammetry investigations. Further insight into the structural characterization of all rhomboidal metallacycles, such as the shape and size, was obtained via molecular simulation by PM6 semiempirical molecular orbital methods.

By combining rigid 120° dicarboxylate donors substituted with [G-0]–[G-3] Frechet-type dendrons and complementary 120° ferrocenyl di-Pt(II) acceptors, a new family of neutral dendritic multiferrocenyl hexagons have been successfully prepared under mild conditions in high yields.

A novel family of hexakis(ferrocenyl) triangles has been successfully constructed from newly designed 60° ferrocenyl building blocks via coordination-driven self-assembly. The structures of all triangles were characterized by multinuclear NMR (1H and 31P), ESI-TOF-MS, and elemental analysis, and their electrochemical behavior has been investigated.

The design and synthesis of a new class of dendritic multiferrocenyl hexagons have been achieved via [3+3] coordination-driven self-assembly. The relative distribution of dendritic and ferrocenyl subunits on the periphery of supramolecular metallocycles can be precisely controlled. The structures of all compounds are confirmed by multinuclear NMR, ESI-MS/ESI-TOF-MS, and elemental analysis. The electrochemical properties of the newly designed dendritic multiferrocenyl complexes have been studied through cyclic voltammetry investigation.