Suzuki-Miyaura cross-coupling reactions were used in the divergent synthesis of a series of 2-arylnaphtho[2,3-b]phosphole P-oxides and their benzo[b]phosphole counterparts. We elucidated the electronic and steric effects of the 2-aryl groups and fused arene moieties on the optical and photophysical properties of these two types of phosphole-based π-systems.
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