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While modifying the shape and size represents a common means to fine\u2010tune 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\u2010carbon structures. Thus, linearly\u2010fused 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\u2010functionalization and properties of new diphosphapentaarene derivatives. 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