Two isomeric [5,6]-pyrrolidine-I h -Sc 3 N@C 80 electron donor acceptor conjugates containing triphenylamine (TPA) as the donor system were synthesized. Electrochemical and photophysical studies of the novel conjugates were made and compared with those of their C 60 analogues, in order to determine i) the effect of the linkage position (N-substituted versus 2-substituted pyrrolidine) of the donor system in the formation of photoinduced charge separated states, ii) the thermal stability towards the retro-cycloaddition reaction and iii) the effect of changing C 60 for I h -Sc 3 N@C 80 as the electron acceptor. It was found that when the donor is connected to the pyrrolidine nitrogen atom, the resulting dyad produces a significantly longer lived radical pair than the corresponding 2-substituted isomer for both the C 60 and I h -Sc 3 N@C 80 dyads. In addition to that, the N-substituted TPA-I h -Sc 3 N@C 80 dyad has much better thermal stability than the 2-subtituted one. Finally, the I hSc 3 N@C 80 dyads have considerably longer lived charge separated states than their C 60 analogues, thus approving the advantage of using I h -Sc 3 N@C 80 instead of C 60 as the acceptor for the construction of fullerene based donor acceptor conjugates. These findings are important for the design and future application of I h -Sc 3 N@C 80 dyads as materials for the construction of plastic organic solar cells.