Doubly N-Confused Calix[6]phyrin Bis-Organopalladium Complexes: Photostable Triplet Sensitizers for Singlet Oxygen Generation

Triplet photosensitizers that generate singlet oxygen efficiently are attractive for applications such as photodynamic therapy (PDT). Extending the absorption band to a near-infrared (NIR) region (700 nm≈) with reasonable photostability is one of the major demands in the rational design of such sensitizers. We herein prepared a series of mono- and bis-palladium complexes (1-Pd-H ₂ , 2-Pd-H ₂ , 1-Pd-Pd, and 2-Pd-Pd) based on modified calix[6]phyrins as photosensitizers for singlet oxygen generation. These palladium complexes showed intense absorption profiles in the visible-to-NIR region (500–750 nm) depending on the number of central metals. Upon photoirradiation in the presence of 1,5-dihydroxynaphthalene (DHN) as a substrate for reactive oxygen species, the bis-palladium complexes generated singlet oxygen with high efficiency and excellent photostability. Singlet oxygen generation was confirmed from the characteristic spectral feature of the spin trapped complex in the EPR spectrum and the intact ¹ O ₂ emission at 1270 nm.