A Dipleiadiene‐Embedded Aromatic Saddle Consisting of 86 Carbon Atoms

Abstract This study presents a new type of negatively curved nanographene (C 86 H 32 ) that contains an unprecedented pattern of heptagons. A tert ‐butylated derivative of C 86 H 32 was successfully synthesized using tetrabenzodipleiadiene as a key building block. This synthesis involved a ring expansion reaction as a key step to form the seven‐membered rings in the framework of tetrabenzodipleiadiene. The single‐crystal structure reveals a saddle‐shaped molecule with a highly bent naphthalene moiety at the center of the polycyclic backbone. As found from the DFT calculations, this aromatic saddle is flexible at room temperature and has a saddle‐shaped geometry as the dominant conformation. The DFT calculations along with experimental results show that the attachment of t ‐butyl groups to the central tetrabenzodipleiadiene moiety of nanographene C 86 H 32 can stabilize the saddle conformation and make this nanographene less flexible.