Photoswitchable Catalysis by a Self-Assembled Molecular Cage.

A heteroleptic [Pd2L2L'2]4+ coordination cage containing a photoswitchable azobenzene-derived ligand catalyzes the Michael addition reaction between methyl vinyl ketone and benzoyl nitromethane within its cavity. The corresponding homoleptic cages are catalytically inactive. The heteroleptic cage can be reversibly disassembled and reassembled using 530 and 405 nm light, respectively, allowing catalysis within the cage to be switched OFF and ON at will.

Real-Time Monitoring of Photoinduced pH Jumps by In Situ Rapid-Scan EPR Spectroscopy.

This work represents the first demonstration of monitoring kinetics upon a light-induced pH jump by in situ rapid-scan (RS) electron paramagnetic resonance (EPR) spectroscopy on the millisecond time scale. Here, we focus on the protonation state of an imidazolidine type radical as a pH sensor under visible light irradiation of a merocyanine photoacid in bulk solution. The results highlight the utility of photoacids in combination with pH-sensitive spin probes as an effective tool for the real-time investigation of biochemical mechanisms regulated by changes in the pH value.