Luminescent 1-1,3-benzazaphospholes.

2-R-1-1,3-Benzazaphospholes (R-BAPs) are an interesting class of σP 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 ( = 0.53) and 3c ( = 0.12) stands in contrast to the weakly emissive methyl substituted analogue 3a ( = 0.08). Comparative computational investigations of 3a-c offer insights into the interplay between structure-function relationships affecting excited state relaxation processes.