Three arylferrocene derivatives, ferrocenylbenzene (MFcB), 1.3-diferrocenylbenzene (DFcB), and 1,3,5-triferrocerylbenzene (TFcB), were prepared and their redox properties systematically explored by thin-layer cyclic voltammetry (CV) and differential-pulse voltammetry (DPV). In contrast to conventional CV measurements that produced only a single pair of redox waves for all three compounds, the thin-layer technique discriminated between the multistep electron-transfer processes of DFcB and TFcB. In particular, two and three pairs of symmetric peaks were observed, respectively, when CV curves were recorded at a graphite electrode coated with a DFcB-containing and a TFcB-containing thin film of nitrobenzene and immersed in aqueous sodium perchlorate solution. These results demonstrate that the ferroceryl moieties attached to the meta-positions of a benzene ring communicate electronically with each other, as a result of their distinct face-to-face orientations. (c) 2008 Elsevier Ltd. All rights reserved.