Two series of phospholes and i,i'biphospholes bearing either 2-or 3-thienyl substituents at the C atoms are prepared by using the Fagan-Nugent route. Their optical (UV/Vis absorption, fluorescence spectra) and electrochemical properties are systematically evaluated. Of particular interest, the first ever reported 3-thienyl-substituted phospholes exhibit higher LUMO levels than their 2-thienyl analogues, and show accordingly different physical properties. This study also re-veals that the i,i'-biphospholes exhibit a-Jt conjugation. The phosphole and i,i '-biphosphole derivatives bearing 3-thienyl substituents are characterized by X-ray diffraction study. The structure-property relationship established following the experimental data are fully supported by theoretical studies including time-dependent(TD)-DF1 spectra. A photocyclization reactioi performed on the thioxo-and oxo phospholes having 3-thienyl substitu ents affords a novel ring-fused phosp hole-thiophene derivative, which wa characterized by an X-ray diffractio study. The structure and electroni properties of this novel dithienophos phole are discussed based on experi mental and theoretical data.
- Densit functional calculations
- Pi interactions
ASJC Scopus subject areas
- Organic Chemistry