Photoswitching Lewis Acid Catalysis with Highly Fatigue Resistant Photochromic Boronates

Photoswitchable Lewis acids represent an untapped frontier in catalysis. Here, we introduce highly fatigue-resistant diarylethene-functionalized boronates and systematically elucidate how substituent patterns govern their photoswitching ability. These Lewis acids feature large tunable affinity amplitudes suitable for on/off control of diverse Lewis acid catalyses and a Lewis base release transformation. Using the emerging framework of global and effective Lewis acidity (gLA and eLA), we demonstrate how photoisomerization divergently modulates both the thermodynamics of Lewis acid-base association and the activation of bound substrates. Unlike irreversible photo Lewis acid generators, the reversibility of this system further allows the photochemical generation of out-of-equilibrium states. These findings highlight the broad potential of photoswitchable boronates for advanced functional applications.