Electrochemical characterisation of tetra- and octa-substituted oxo(phthalocyaninato)titanium(IV) complexes

Tau, P.L. and Nyokong, T. (2007) Electrochemical characterisation of tetra- and octa-substituted oxo(phthalocyaninato)titanium(IV) complexes. Electrochimica Acta, 52 (11). pp. 3641-3650. ISSN 0013-4686

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Official URL: http://dx.doi.org/10.1016/j.electacta.2006.10.023

Abstract

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 Ti[superscript IV]Pc[superscript 2−]/Ti[superscript III]Pc[superscript 2−] and Ti[superscript III]Pc[superscript 2−]/Ti[superscript II]Pc[superscript 2−] redox processes and the last two reductions are ring-based processes due to Ti[superscript II]Pc[superscript 2−]/Ti[superscript II]Pc[superscript 3−] and Ti[superscript II]Pc[superscript 3−]/Ti[superscript II]Pc[superscript 4−]. Chronocoulometry 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.

Item Type:Article
Uncontrolled Keywords:Titanium tetraphthalocyanines; Octaphthalocyanine; Peripheral; Non-peripheral; Cyclic voltammetry; Spectroelectrochemistry
Subjects:Y Unknown > Subjects to be assigned
Divisions:Faculty > Faculty of Science > Chemistry
ID Code:503
Deposited By: Mrs Eileen Shepherd
Deposited On:16 Mar 2007
Last Modified:01 Aug 2012 12:50
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