Two series of binuclear macrocyclic nickel(II) complexes with varying lengths of the chain linking the two macrocyclic rings were characterised by cyclic voltammetry under argon and CO2. The first series consisted of binuclear complexes [Ni2L2-6](4+) containing pentaaza macrocycles with (CH2)(n) bridges (n = 2, 3, 4, 6) or a p-xylyl linkage (L-6). In general, the two nickel sites in the binuclear complexes behave independently with the currents corresponding to the simultaneous transfer of two electrons. The redox potentials are remarkably constant along this series, but the peak separations increase, reflecting slower electron transfer due to more effective adsorption on the electrode. Electrochemical data for the electrocatalytic reduction of CO2 in MeCN/10% H2O revealed catalytic waves for CO2 reduction with EF, close to - 1.7 V and catalytic currents (i(p)(c)) which are about half those of the mononuclear complex, proposed to be due to steric constraints allowing strong interaction of only one nickel centre of the binuclear one on the surface. The catalytic currents increased slightly as the linking chain length increased as the stereochemical constrains were relaxed somewhat. There was also a splitting in the catalytic peaks of the bismacrocyclic complexes which could reflect two types of adsorbed catalyst sites. In the more sterically crowded series of complex, [Ni2L7](4+) along with the series of linked heptaaza macrocyclic complexes [Ni2L9-11](4+) much more positive redox potentials were observed due to both alkylation of the coordinated nitrogen atoms, which decreases the ligand field, and the introduction of steric barriers to axial coordination. These steric barriers prevented strong electrode interaction and led to a lower catalytic activity. Indeed, the complex [Ni2L7](4+) did not even show any interaction with CO2 in dry acetonitrile. The complexes showed well separated peaks due to solution and surface catalytic activity, and the surface catalytic currents were now comparable to mononuclear complexes at the same effective concentration. We proposed that the less effective absorption on the electrode arising from ligand steric interactions places far fewer stereochemical constraints on the adsorption of both nickel centres to the same extent as the binuclear complex, and hence the catalytic currents for binuclear complex and mononuclear complex are comparable. (C) 2000 Elsevier Science Ltd. All rights reserved.