An imidazoacridine-based TADF material as an effective organic photosensitizer for visible-light-promoted [2 + 2] cycloaddition
Ethan R. Sauvé, Don M. Mayder, Saeid Kamal, Martins S. Oderinde, Zachary M. Hudson
Abstract
Energy transfer (EnT) is a fundamental activation process in visible-light-promoted photocycloaddition reactions. This work describes the performance of imidazoacridine-based TADF materials for visible-light mediated triplet-triplet EnT photocatalysis. The TADF material ACR-IMAC has been discovered as an inexpensive, high-performance organic alternative to the commonly used metal-based photosensitizers for visible-light EnT photocatalysis. The efficiency of ACR-IMAC as a photosensitizer is comparable with Ir-based photosensitizers in both intra- and intermolecular [2 + 2] cycloadditions. ACR-IMAC mediated both dearomative and non-dearomative [2 + 2] cycloadditions in good yields, with high regio- and diastereocontrol. Cyclobutane-containing bi- tri- and tetracylic scaffolds were successfully prepared, with broad tolerance toward functional groups relevant to drug discovery campaigns. Fluorescence quenching experiments, time-correlated single-photon counting, and transient absorption spectroscopy were also conducted to provide insight into the reaction and evidence for an EnT mechanism.