Novel hexabutylsulphonyltribenzotetraazachlorin–fullerene (C60) complexes of iron (FeHBSTBTAC–C60) and cobalt (CoHBSTBTAC–C60) have been synthesized and their electrochemistry and oxygen reduction reaction (ORR) compared with their octabutylsulphonylphthalocyanine analogues (FeOBSPc and CoOBSPc). It is proved that electron-withdrawing substituents (–SO2Bu and C60) on phthalocyanine macrocycle exhibit distinct impact on the solution electrochemistry of these metallophthalocyanine (MPc) complexes. The more electron-withdrawing C60 substituent suppressed ORR compared to the –SO2Bu in alkaline medium. FeOBSPc showed the best ORR activity involving a direct 4-electron mechanism, a rate constant of ~1 x 108 cm3 mol-1 s-1 and a Tafel slope of -171 mV dec-1.
Reference:
Ozoemena, KI, Mamuru, SA, Fukuda, T, Kobayashi, N and Nyokong, T. 2009. Metal (Co, Fe) tribenzotetraazachlorin-fullerene conjugates: impact of direct p-bonding on the redox behaviour and oxygen reduction reaction. Electrochemistry Communications, Vol. 11(6). pp 1221-1225
Ozoemena, K., Mamuru, S., Fukuda, T., Kobayashi, N., & Nyokong, T. (2009). Metal (Co, Fe) tribenzotetraazachlorin-fullerene conjugates: impact of direct p-bonding on the redox behaviour and oxygen reduction reaction. http://hdl.handle.net/10204/3583
Ozoemena, KI, SA Mamuru, T Fukuda, N Kobayashi, and T Nyokong "Metal (Co, Fe) tribenzotetraazachlorin-fullerene conjugates: impact of direct p-bonding on the redox behaviour and oxygen reduction reaction." (2009) http://hdl.handle.net/10204/3583
Ozoemena K, Mamuru S, Fukuda T, Kobayashi N, Nyokong T. Metal (Co, Fe) tribenzotetraazachlorin-fullerene conjugates: impact of direct p-bonding on the redox behaviour and oxygen reduction reaction. 2009; http://hdl.handle.net/10204/3583.