By means of arene ligand exchange of the triple deckers [{(eta(5)-R1-5C5)CO}(2)-(mu)-(eta(4):eta(4)-toluene)] (R1-5 = Me, R1-3 = tert-butyl) at room temperature a number of mono-, di-, and tri-nuclear sandwich complexes of the polycondensed aromatics polycyclic aromatic hydrocarbons (PAHs) tetracene, benzo[a]pyrene, perylene, triphenylene and benzo[a]triphenylene have been synthesized. For triphenylene and benzo[b]triphenylene however, a threefold coordination of [(eta(5)-C5Me5)Co] fragments in the periphery of these PAHs is found, tetracene allows for a twofold coordination of two [(eta(5)-C5Me5)Co fragments in the ring periphery leaving a central naphthalene unit of this PAH uncomplexed. Perylene serves as a twofold coordination site for [(eta(5)-1,2,4 tri-tert-butyl-C5H2)Co] fragments which are coordinated in each of the two naphthalene fragments of this pi-perimeter. (C) 2003 Elsevier Science B.V. All rights reserved.