Superextended tetrathiafulvalene compounds were prepared by the substitution of gem-dichlorovinylene with 1,2-benzenedithiol. This strategy allowed for the efficient synthesis of a highly π-extended 9,10-bis(benzo-1,3-dithiol-2-ylidene)-9,10-dihydroanthracene (sExTTF) moiety, which exhibits an intense light absorption in the visible spectrum and a reversible oxidation process. A macrocyclic host for fullerenes containing two sExTTF units was synthesized. Complexation studies revealed that fullerenes promote the photooxidation of the 1,3-dithiolylidene bond. This grants new insights into the nature of the low-energy band that appeared in several reports on fullerene complexation with hosts containing the 1,3-dithiolylidene moiety.