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Red-phosphorescent bis-cyclometalated iridium compounds with salicylaldimine, 2-picolinamide, and related ancillary ligand classes are described; the 2-picolinamide analogues exhibit multiple binding modes that influence photophysical properties.

 

This perspective focuses on strategies to manipulate and optimize three key determinants of metal-based molecular photosensitizers – the absorption profile, the excited-state redox potentials, and the excited-state lifetime.

 

A strongly photoreducing iridium photosensitizer enables diverse, additive-free reductive photoredox transformations on challenging ketone and imine substrates.

 

2-R-1 H -1,3-Benzazaphospholes (R-BAPs) are an interesting class of σ 2 P heterocycles containing PC bonds. While closely related 2-R-1,3-benzoxaphospholes (R-BOPs) have been shown to be highly photoluminescent materials depending on specific R substituents, photoluminescence of R-BAPs has been previously limited to an example having a fused carbazole ring system. Here we detail the synthesis and structural characterization of a new R-BAP (3c, R = 2,2′-dithiophene), and compare its photoluminescence against two previously reported R-BAPs (3a, R, R′ = Me and 3b, R = 2-thiophene). The significant fluorescence displayed by the thiophene derivatives 3b ( φ = 0.53) and 3c ( φ = 0.12) stands in contrast to the weakly emissive methyl substituted analogue 3a ( φ = 0.08). Comparative computational investigations of 3a–c offer insights into the interplay between structure–function relationships affecting excited state relaxation processes.