Selectivity‐Enhanced Near‐Infrared Photocatalytic Dehydrogenation and C─N Coupling via Lanthanide Nanocrystal‐Mediated Photosensitization

Abstract Near‐infrared (NIR) light‐driven photocatalysis provides a promising solution to the inherent limitations of conventional ultraviolet (UV) and visible‐light photocatalysis, such as shallow penetration, photodamage from high‐energy irradiation, and limited selectivity. However, effective strategies for achieving NIR photocatalysis remain scarce. Here, a novel strategy that achieves NIR photocatalysis with significantly enhanced selectivity is reported through lanthanide nanocrystal‐mediated photosensitization. A composite nanocatalyst, comprising NaNdF ₄ lanthanide nanocrystals and Zn(II) phthalocyanine organic photosensitizers is designed, where the NaNdF ₄ absorb 808 nm NIR light and transfer energy directly to the photosensitizers via lanthanide‐mediated triplet sensitization. This approach enables selective functionalization of organic substrates with increased yields and reduced side‐product formation compared to UV/visible light excitation. The enhanced selectivity arises from the controlled generation of superoxide anions (O ₂ ⁻ ) as reactive oxygen species (ROS) and minimized substrate photoactivation. The approach enables targeted dehydrogenation and C─N coupling reactions of diverse N‐heterocyclic substrates, including halogen‐substituted compounds that are typically prone to undesired side reactions. The findings establish a versatile strategy for improving selectivity in photocatalytic transformations, opening new opportunities in light‐sensitive organic synthesis and sustainable catalysis.