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On-Surface Synthesis of Antiaromatic and Open-Shell Indeno[2,1‑b]fluorene Polymers and Their Lateral Fusion into Porous Ribbons

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posted on 29.07.2019, 04:29 by Marco Di Giovannantonio, Kristjan Eimre, Aliaksandr V. Yakutovich, Qiang Chen, Shantanu Mishra, José I. Urgel, Carlo A. Pignedoli, Pascal Ruffieux, Klaus Müllen, Akimitsu Narita, Roman Fasel
Polycyclic hydrocarbons have received great attention due to their potential role in organic electronics and, for open-shell systems with unpaired electron densities, in spintronics and data storage. However, the intrinsic instability of polyradical hydrocarbons severely limits detailed investigations of their electronic structure. Here, we report the on-surface synthesis of conjugated polymers consisting of indeno­[2,1-b]­fluorene units, which are antiaromatic and open-shell biradicaloids. The observed reaction products, which also include a nonbenzenoid porous ribbon arising from lateral fusion of unprotected indeno­[2,1-b]­fluorene chains, have been characterized via low-temperature scanning tunneling microscopy/spectroscopy and noncontact atomic force microscopy, complemented by density-functional theory calculations. These polymers present a low band gap when adsorbed on Au(111). Moreover, their pronounced antiaromaticity and radical character, elucidated by ab initio calculations, make them promising candidates for applications in electronics and spintronics. Further, they provide a rich playground to explore magnetism in low-dimensional organic nanomaterials.