Straightforward Access to Multifunctional π‐Conjugated P‐Heterocycles Featuring an Internal Ylidic Bond

• Published in: Angewandte Chemie International Edition Vol. 61; no. 31; pp. e202205548 - n/a
• Main Authors: Delouche, Thomas, Caytan, Elsa, Cordier, Marie, Roisnel, Thierry, Taupier, Grégory, Molard, Yann, Vanthuyne, Nicolas, Le Guennic, Boris, Hissler, Muriel, Jacquemin, Denis, Bouit, Pierre‐Antoine
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 01.08.2022; Wiley Subscription Services, Inc; Wiley-VCH Verlag; John Wiley and Sons Inc
• Edition: International ed. in English
• Subjects: Chemical Sciences; Chemistry; Chemistry, Multidisciplinary; Optical properties; Organic chemistry; Physical Sciences; Redox properties; Science & Technology; PHOSPHONIUM-IODONIUM YLIDES; SALTS; CYCLIZATION
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202205548

We report the straightforward one‐pot synthesis of novel 5‐ or 6‐membered P‐heterocycles featuring an internal ylidic bond: P‐containing acenaphthylenes and phenanthrenes. The stability of the compounds tolerates post‐functionalization through direct arylation to introduce electron‐rich/poor substituents and the synthetic strategy is also compatible with the preparation of more elaborate polyaromatic scaffolds such as acenes and helicenes. Using a joint experimental (X‐ray analysis, optical and redox properties) and theoretical approach, we perform a full structure–property relationships study on these new platforms. In particular, we show that molecular engineering allows not only tuning their absorption/emission across the entire visible range but also endowing them with chiroptical or non‐linear optical properties, making them valuable dyes for a large panel of photonic or opto‐electronic applications. A simple synthesis of P‐heterocycles featuring an internal ylidic bond is reported. The stability of the compounds tolerates post‐functionalization (direct arylation) and the strategy is also compatible with the preparation of polyaromatic scaffolds (acenes, helicenes). Molecular engineering allows tuning the optical and redox properties, making them valuable dyes for a large panel of photonic or opto‐electronic applications.