Abstract:

Photoisomerization of azobenzenes from their stable E isomer to the metastable Z state is the basis of numerous applications of these molecules. However, this reaction typically requires ultraviolet light, which limits applicability. In this study, we introduce disequilibration by sensitization under confinement (DESC), a supramolecular approach to induce the E-to-Z isomerization by using light of a desired color, including red. DESC relies on a combination of a macrocyclic host and a photosensitizer, which act together to selectively bind and sensitize E-azobenzenes for isomerization. The Z isomer lacks strong affinity for and is expelled from the host, which can then convert additional E-azobenzenes to the Z state. In this way, the host?photosensitizer complex converts photon energy into chemical energy in the form of out-of-equilibrium photostationary states, including ones that cannot be accessed through direct photoexcitation. Chemists often strive to push reactions metaphorically uphill toward less energetically favorable products. The challenge is to keep those products from rolling right back down. Gemen et al. report a clever tactic for twisting azobenzene into its higher-energy Z conformation. Specifically, they lured the more stable E isomer into a supramolecular host, along with a photosensitizer. When visible light injects energy to induce the twist, the Z isomer no longer fits in the cavity, so it gets pushed out before more light can twist it back. ?Jake S. Yeston Spatial constraints in a supramolecular host selectively convert azobenzenes to their metastable state under visible light.Photoisomerization of azobenzenes from their stable E isomer to the metastable Z state is the basis of numerous applications of these molecules. However, this reaction typically requires ultraviolet light, which limits applicability. In this study, we introduce disequilibration by sensitization under confinement (DESC), a supramolecular approach to induce the E-to-Z isomerization by using light of a desired color, including red. DESC relies on a combination of a macrocyclic host and a photosensitizer, which act together to selectively bind and sensitize E-azobenzenes for isomerization. The Z isomer lacks strong affinity for and is expelled from the host, which can then convert additional E-azobenzenes to the Z state. In this way, the host?photosensitizer complex converts photon energy into chemical energy in the form of out-of-equilibrium photostationary states, including ones that cannot be accessed through direct photoexcitation. Chemists often strive to push reactions metaphorically uphill toward less energetically favorable products. The challenge is to keep those products from rolling right back down. Gemen et al. report a clever tactic for twisting azobenzene into its higher-energy Z conformation. Specifically, they lured the more stable E isomer into a supramolecular host, along with a photosensitizer. When visible light injects energy to induce the twist, the Z isomer no longer fits in the cavity, so it gets pushed out before more light can twist it back. ?Jake S. Yeston Spatial constraints in a supramolecular host selectively convert azobenzenes to their metastable state under visible light.

Notes:

doi: 10.1126/science.adh9059