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.

Light-Controlled Regioselective Synthesis of Fullerene Bis-Adducts

Demitri N.;Silvi S.;Arcudi F.;Prato M.
2021

Abstract

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.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11368/2992069
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