Dithiafulvenyl‐Extended N ‐Heterotriangulenes and Their Interaction with C 60 : Cooperative Fluorescence

We describe the synthesis as well as the electronic and photophysical characterization of novel N ‐heterotriangulene derivatives decorated with methoxycarbonyl‐ and methyl‐sulfanyl‐substituted dithiafulvenyl moieties. The association of these electron‐rich compounds with fullerene C 60 as electron acceptor was investigated by means of photophysical, voltammetric, and mass spectrometric methods and rationalized by DFT calculations. Importantly, light‐induced interactions between the dithiafulvene‐substituted N ‐heterotriangulene bearing methoxycarbonyl substituents with C 60 leads to cooperative fluorescence. Quantitative Job plot analyses by means of fluorescence spectroscopy and voltammetry confirm a 1:1 association with binding constants in the order of 10 4   m −1 . Supportive results for the supramolecular assembly of both N ‐heterotriangulenes with C 60 were obtained by ESI mass spectrometric investigations in the gas phase.