Osmium bipyridine complexes were directly grafted to carbon electrodes through electroreduction of the diazonium salts [Os(bpy-ph-N-2(+))(3)](PF6)(5) (1) and [Os(bpy-ph-N-2(+))(2)Cl-2](PF6)(2) (2). Growth of the films was not self-limiting as is usually found for grafting from diazonium salts. It appears that electron hopping through the bipyridine ligands of the immobilised complexes enables film growth to continue at a constant rate during grafting by potential cycling. The surface concentrations of deposited films were measured electrochemically and the film thicknesses were measured by depth-profiling using the atomic force microscope. Films up to 42 nm thick were prepared with no evidence for slowing of film growth. The grafted films exhibited high stability when repetitively cycled through the Os2+/3* couple and electron transfer rate constants of 11.4 s(-1) and 35.4 s(-1) were measured in ACN and PBS, respectively, for the Os2+/3+ couple of the film grafted from 1. (C) 2010 Elsevier Ltd. All rights reserved.