Facile Access to Phosphorus Ylide-fused Heteroarenes Possessing Tunable Optoelectronic Properties and High Nonlinear Optical Performances.

We report here a novel family of ylidic P-heteroarenes (P1-P6), structurally featuring unique phosphonium cyclopentadienylide (P-Cp)-fused π-skeletons and synthetically prepared via an unexpected one-pot [2+3]/[3+3] phospha-annulation reaction. While the facile and modular synthesis allows the fine-tuning of their optical absorptions and redox properties, single-crystallographic and theoretical analysis of these P-heteroarenes further reveal that the fusion of P-Cp moiety leads to substantial intramolecular charge-separated features with high ylidic character values of up to 84 %. Benefitted from such dipolar structures, these P-heteroarenes not only allows stepwise electrophilic substitution reaction for further structural π-expansions, but also exhibit excellent nonlinear optical (NLO) responses and optical limiting (OL) performances comparable to or exceed those of C. As a model compound, the persistent radical-anion salt of P5a was also prepared through chemical reduction, thus offering valuable insights into the electronic structures of reduced P-ylidic species. Our work not only established a highly efficient synthetic method toward new P-heteroarenes, but also provide fundamental understanding of those fused-ring ylidic P-heterocycles with promising NLO/OL applications.