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Despite their unique structures, the synthesis of CAs is challenging, and until recently, the largest CA molecule synthesized was circumanthracene. In this study, we report the successful synthesis of an extended circumpentacene derivative <jats:bold>1<\/jats:bold>, which represents the largest CA molecule synthesized to date. Its structure was confirmed by X\u2010ray crystallographic analysis and its electronic properties were systematically investigated by both experiments and theoretical calculations. It shows a unique open\u2010shell diradical character due to the existence of extended zigzag edges, with a moderate diradical character index (<jats:italic>y<\/jats:italic><jats:sub>0<\/jats:sub>=39.7\u2009%) and a small singlet\u2010triplet energy gap (\u0394<jats:italic>E<\/jats:italic><jats:sub>S\u2010T<\/jats:sub>=\u22124.47\u2005kcal\/mol). It exhibits a dominant local aromatic character with \u03c0\u2010electrons delocalized in the individual aromatic sextet rings. It has a small HOMO\u2013LUMO energy gap and displays amphoteric redox behavior. The electronic structures of its dication and dianion can be considered as doubly charged structures in which two coronene units are fused with a central aromatic benzene ring. This study provides a new route toward stable multizigzag\u2010edged graphene\u2010like molecules with open\u2010shell di\/polyradical character.<\/jats:p>","DOI":"10.1002\/anie.202306938","type":"journal-article","created":{"date-parts":[[2023,6,20]],"date-time":"2023-06-20T11:30:51Z","timestamp":1687260651000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":38,"title":["Circumpentacene with Open\u2010Shell Singlet Diradical Character"],"prefix":"10.1002","volume":"62","author":[{"given":"Qing","family":"Jiang","sequence":"first","affiliation":[{"name":"Department of Chemistry National University of Singapore  3 Science Drive 3 Singapore 117543 Singapore"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Haipeng","family":"Wei","sequence":"additional","affiliation":[{"name":"Department of Chemistry National University of Singapore  3 Science Drive 3 Singapore 117543 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