π‐Extended <i>peri</i>‐Acenes: Recent Progress in Synthesis and Characterization

Abstract Nanographenes (NGs) with open‐shell character have gained intense attention due to their potential applications in future organic nanoelectronics and spintronics. Among them, NGs bearing a pair of parallel zigzag edges, such as acenes peri ‐acenes (PAs) bestow unique (opto)electronic magnetic properties owing localized non‐bonding π‐state. However, reactive edges impart intrinsic instability, leading the challenging synthesis. The recent development synthetic strategies provided access several π‐extended PAs, which were considered unrealistic for decades. Notably, laterally structures zigzag‐edged graphene nanoribbons was realised via on‐surface synthesis PAs solution is still its infancy, more intensive scientific efforts are needed surpass existing challenges regarding stability solubility. This Review provides an overview progress characterization through bottom‐up strategy, including solution‐phase chemistry. In addition, views on prospects also provided.