Light-Induced Increasein Bond StrengthfromChalcogen Bond to Three-Electron σ Bond upon Excitation

Chalcogen bonds are σ hole interactions between a chalcogen center and a Lewis base center and have been applied in recent years as an alternative to hydrogen bonds in supramolecular chemistry and catalysis. While the electronic interactions of chalcogen bonds in the ground state have been intensively analyzed, there is barely any knowledge about the electron structure in the excited state. This is despite the fact that in some cases photoswitches containing chalcogen bonds exhibit exceptional switching behavior. Here, we investigate the effect of light absorption on chalcogen bonds containing divalent chalcogen centers. Quantum chemical calculations reveal that in the excited S₁ state the noncovalent chalcogen bond converts to a covalent three-electron σ bond. The bond between the chalcogen center and the Lewis base center is thus significantly reinforced by light excitation. This change in bond type explains the previously experimentally observed nonswitchability of some tellurium-containing azo compounds. Furthermore, we were able to demonstrate that the switchability of certain selenium-containing compounds is temperature-dependent, whereby the ratio of the less stable <i>cis</i> compound is higher for higher temperatures. These results highlight the potential for designing responsive materials and dynamic molecular systems based on light-induced chalcogen bond modulation.