Straightforward Access to Multifunctional π‐Conjugated P‐Heterocycles Featuring an Internal Ylidic Bond**
Thomas Delouche, Elsa Caytan, Marie Cordier≈, Thierry Roisnel, Grégory Taupier, Yann Molard, Nicolas Vanthuyne, Boris Le Guennic, Muriel Hissler, Denis Jacquemin, Pierre‐Antoine Bouit
Abstract
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.