Dismantling the Hyperconjugation of π-Conjugated Phosphorus Heterocycles

The development of π-extended phosphorus heterocycles has been rapidly increasing because of their unique optoelectronics properties, which are very often considered to be a consequence of special hyperconjugative interactions. However, the latter interactions have primarily been investigated within the five-membered species, phospholes, and they are often conceptually extrapolated to the rest of π-extended phosphorus heterocycles (including six-membered P-heterocycles) despite evident structural differences. Herein, we report, for the first time, a detailed investigation that sheds light on the hyperconjugative effects of a series of phosphorus heterocyclic systems by means of EDA and NBO calculations within a DFT framework. Our results lay the foundations for the future design of π-extended phosphorus heterocycles with improved optoelectronics properties.