On the reactivity of P-chloro dithieno[3,2-b:2′,3′-d]phosphole oxide

The P-functionalization of dithieno[3,2-b:2′,3′-d]phosphole oxides via reaction of a P-chloro derivative with aromatic amines and alcohols is reported. The reactions proceed rapidly and provide the products in good yields, highlighting the synthetic versatility of the P-chloro dithienophosphole oxide toward effectively modifying the molecular scaffold without the need for elaborate phosphorus precursor syntheses. The resulting phosphinic amide and ester products show interesting photophysics that strongly depend on the nature of the P-substituent such as high luminescence quantum yields for the ester derivatives, as well as aggregation-induced enhanced emission for the amide derivative. The phosphinic amide species also shows intriguing self-assembly in the solid state via hydrogen bonding.