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A library of nitrogen\u2010containing extended PDIs was synthesized via an aza\u2010benzannulation reaction followed by a Pd\u2010catalysed <jats:italic>ortho<\/jats:italic>\u2010pentannulation reaction. <jats:italic>Ortho<\/jats:italic>\u2010pentannulated BACDs revealed strong aggregation abilities in solution. Concentration\u2010dependent UV\/Vis absorption spectra, variable temperature <jats:sup>1<\/jats:sup>H NMR experiments, and atomic force microscopy coupled to molecular dynamics support their self\u2010assembly into columnar aggregates. Cyclic voltammetry experiments in dichloromethane reveal prominent splitting of the first reduction wave, attributed to the formation of unprecedented intermolecular anionic MV and \u03c0\u2010dimers in organic solvent. These species were thoroughly characterized by real\u2010time spectroelectrochemistry, electrochemical simulations and theoretical calculations. Remarkably, this work underscores the tuneable nature of AzaBenzannulatedPerylene Diimides (AzaBPDIs) and BACDs, emphasizing their potential as a promising scaffold for designing supramolecular materials with long\u2010range radical anion delocalization. The observation of this phenomenon provides insights into the fundamental behaviour of supramolecular organic semiconductors, thereby paving the way for the development of novel electronic devices and electron\u2010deficient materials.<\/jats:p>","DOI":"10.1002\/anie.202413616","type":"journal-article","created":{"date-parts":[[2024,8,20]],"date-time":"2024-08-20T16:29:35Z","timestamp":1724171375000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Intermolecular Anionic Mixed\u2010Valence and \u03c0\u2010Dimer Complexes of <i>ortho<\/i>\u2010Pentannulated Bisazacoronene Diimide"],"prefix":"10.1002","volume":"64","author":[{"given":"Arthur H. 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