The synthesis and electrochemical characterisation of the following oxotitanium tetra-substituted phthalocyanines are reported: 1,(4)(tetrabenzyloxyphthalocyaninato)titanium(IV) oxide (5a); 1,(4)-{tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato}titanium(IV) oxide (5b); 2,(3)(tetrabenzyloxyphthalocyaninato)titanium(IV) oxide (6a) and 2,(3)-{tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato}titanium(IV) oxide (6b). The electrochemical characterisation of complexes octa-substituted with 4-(benzyloxy)phenoxy (9b), phenoxy (9c) and tert-butylphenoxy (9d) groups is also reported. The cyclic voltammograms of the complexes exhibit reversible couples I-III and couple IV is quasi-reversible for complexes 5a, 5b, 6a and 6b. The first two reductions are metal-based processes, confirmed by spectroelectrochemistry to be due to (TiPc2)-Pc-IV-/(TiPc2-)-Pc-III and (TiPc2-)-Pc-III/(TiPc2-)-Pc-II redox processes and the last two reductions are ring-based processes due to (TiPc2)-Pc-II-/(TiPc3-)-Pc-II and (TiPc3-)-Pc-II/(TiPc4-)-Pc-II. Chrono-coulometry confirmed a one-electron transfer at each reduction step. The electrochemistry of the above complexes is also compared to the previously reported 5c, 5d, 6c and 6d. (c) 2006 Elsevier Ltd. All rights reserved.