Two "self-complexing" macrocycles (22ab and 23ab) based complexation between the two separated components, i.e. the cyclic acceptor 3 and the tetrakis(methylthio)-on a methylthio-substituted derivative of the electron donor tetrathiafulvalene (TTF) and a cyclic bipyridinium acceptor tetrathiafulvalene 6, was not observed by 1 H-NMR spectroscopy. However, 3 was able to bind unsubstituted TTF have been prepared. [1] When "decomplexed" by fractional crystallization, the rigid compound 22b was not able to (5) in its cavity, albeit with a small association constant of only 60 M -1 . Taking advantage of the tetravalency of TTF, we undergo "recomplexation" to any significant degree, whereas for the more flexible 23b, an equilibrium between also report the synthesis of a "self-complexing" pyromellitic diimide/TTF macrocycle (33ab). Whereas 22ab and 23ab "complexed" (23a) and "uncomplexed" (23b) compounds was slowly re-established in solution according to UV/Vis were prepared employing the concept of template-assisted synthesis, [2] the synthesis of 33ab did not rely on this measurements. 23ab was thus seen to behave as a "thermoswitch", although with a rather slow response. Any technique.