Structural and Electronic Impacts of the Axial Substitution at the Phosphorus Center of C(sp3)‐Bridged P‐Heterotriangulenes

Abstract

AbstractThe structural and electronic properties of the dimethylmethylene‐bridged P‐heterotriangulene have been systematically modulated by functionalization of its phosphorus center. The optoelectronic properties of the obtained derivatives in solution were characterized by UV/Vis absorption and emission spectroscopy, cyclic voltammetry and 31P NMR spectroscopy. The solid state structures were analyzed by X‐ray crystallography. The experimental results were corroborated by density functional theory calculations which revealed the crucial influence of the axial substitution on the bowl‐shaped geometry of the phosphorus‐centered polycyclic scaffold, which is proportional to the s‐character of the P−X bond. The advantage of the bowl‐shaped P‐heterotriangulene scaffold was demonstrated by successful co‐crystallization with fullerene C60.