We report the synthesis, structural characterisation andsolution-phase dynamics of a series of polyaromatic hydrocarbon complexes of the 12-electron {Rh(PiBu3)2}+ fragment. Crystal structures of this fragment with benzene, naphthalene, anthracene, pyrene, triphenylene and coronene are described, alongside their solution NMR spectroscopic data. The ligands map out a systematic increase in size of the aromatic subunit, and represent an approach to the limiting case of coordination to a graphene surface. The solid-state and solution structures of a {Rh(COD)}+ fragment coordinated to a hexa-peri-hexabenzocoronene are also reported. A range of polyaromatic hydrocarbons of increasing size (naphthalene through coronene) have been prepared and their solid-state and solution structures investigated. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA.
