Linearly-fused polyarenes are an important class of compounds with high relevance in materials science. While modifying the shape and size represents a common means to fine-tune their properties, the precise placement of heteroatoms is a strategy that is receiving an increasing deal of attention to overcome the intrinsic limitations of all-carbon structures. Thus, linearly-fused diphosphaarenes recently emerged as a novel family of molecules with striking optoelectronic properties and outstanding stability. However, the properties of diphosphaarenes are far from being benchmarked. Herein, we report the synthesis, phosphorus post-functionalization and properties of new diphosphapentaarene derivatives. We describe their synthetic limitations and unveil their potential for optoelectronic applications.
