Synthesis of a Luminescent Azaphosphole

• Published in: European journal of inorganic chemistry Vol. 2016; no. 5; pp. 768 - 773
• Main Authors: Wu, Shanshan, Rheingold, Arnold L., Golen, James A., Grimm, Alexandra B., Protasiewicz, John D.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.02.2016; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: Benzazaphospholes; Carbazoles; Chemistry; Chemistry, Inorganic & Nuclear; Chlorides; Displays; Fluorescence; Heterocycles; Mathematical analysis; Mathematical models; Organophosphorus compounds; Phosphaalkenes; Phosphines; Physical Sciences; Science & Technology; Synthesis; Heterocycles; Phosphaalkenes; SUBSTITUTED 1,3-BENZAZAPHOSPHOLES; SOLAR-CELLS; Fluorescence; Benzazaphospholes; PHOTOPHYSICAL PROPERTIES; LIGHT-EMITTING-DIODES; HYBRID LIGANDS; LIGANDS SYNTHESIS; Organophosphorus compounds; PHOSPHA-ORGANIC CHEMISTRY; DERIVATIVES; METALATED 1,3-AZAPHOSPHOLES
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201501279

A carbazole‐based azaphosphole (compound 3) has been prepared by acid‐catalyzed dehydrocyclization of 1‐phosphino‐9H‐carbazole (2) with benzoyl chloride. Unlike other benzazaphospholes having σ2,λ3‐multiply bonded phosphorus atoms, compound 3 displays significant fluorescence in solution, as does primary phosphine 2. Compound 3, as well as the materials on route to its synthesis, were characterized by multinuclear NMR, UV/Vis, and fluorescence spectroscopy. The optical data of 2 and 3 are consistent with results of DFT and TDDFT [6‐311G+(d,p) CAMB3LYP] calculations. The computed structure of compound 3′ (R = Ph) is also consistent with the experimental X‐ray structural determination, which reveals a planar heterocyclic system and slight rotation of the p‐tolyl group out of plane with respect to the heterocyclic core. A carbazole‐based azaphosphole (compound 3) has been prepared by acid‐catalyzed dehydrocyclization of 1‐phosphino‐9H‐carbazole (2) with benzoyl chloride. Compounds 2 and 3 display significant fluorescence in solution.