Luminescent 1H-1,3-benzazaphospholes

2-R-1H-1,3-Benzazaphospholes (R-BAPs) are an interesting class of σ(2)P heterocycles containing P[double bond, length as m-dash]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.