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Activating photosensitizers with long-wavelength excitation is an important parameter for effective photodynamic therapy due to the minimal toxicity of this light, its superior tissue penetration, and excellent spatial resolution. Unfortunately, most Ir(III) complexes suffer from limited absorption within the phototherapeutic window, rendering them ineffective against deep-seated and/or large tumors, which poses a significant barrier to their clinical application. To address this issue, several efforts have been recently made to shift the absorption of Ir(III) photosensitizers to the deep-red/near-infrared region by using different strategies: functionalization with organic fluorophores, including porphyrinoid compounds, and ligand design via π-extension and donor–acceptor interactions. In this Frontier, we highlight such new developments and the ongoing challenges in this field. [ABSTRACT FROM AUTHOR]

A highly regio-, enantio- and diastereo-selective strategy involving initial enantioselective conjugate addition to 4-nitro-5-styrylisoxazoles serves as a key step for the desymmetrization of 2,5-cyclohexadienones has been disclosed. We have designed a new class of 2,5-cyclohexadienones appended with 4-nitro-5-styrylisoxazoles to undergo organocatalytic asymmetric double or triple conjugate addition in a domino sequence depending on the substrate type leading to desymmetrization of the 2,5-cyclohexadienone core. The developed protocol allows the construction of a valuable hydrophenanthrene core or a unique bridged scaffold bearing multiple chiral centers with excellent enantio- (up to >99.5 : 0.5 er) and diastereo-control for diverse substrates. [ABSTRACT FROM AUTHOR]