Light-Controlled Regioselective Synthesis of Fullerene Bis-Adducts

Multi-functionalization and isomer-purity of fullerenes are crucial tasks for the development of their chemistry in various fields. In both current main approaches—tether-directed covalent functionalization and supramolecular masks—the control of regioselectivity requires multi-step synthetic procedures to prepare the desired tether or mask. Herein, we describe light-responsive tethers, containing an azobenzene photoswitch and two malonate groups, in the double cyclopropanation of [60]fullerene. The formation of the bis-adducts and their spectroscopic and photochemical properties, as well as the effect of azobenzene photoswitching on the regiochemistry of the bis-addition, have been studied. The behavior of the tethers depends on the geometry of the connection between the photoactive core and the malonate moieties. One tether lead to a strikingly different adduct distribution for the E and Z isomers, indicating that the covalent bis-functionalization of C60 can be controlled by light.