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Static Scanning Tunneling Microscopy Images Reveal the Mechanism of Supramolecular Polymerization of an Oligopyridine on Graphite.

Felix D GollGerhard TaubmannUlrich Ziener
Published in: Angewandte Chemie (International ed. in English) (2022)
Supramolecular polymerization of a donor-acceptor bisterpyridine (BTP) equipped with an electron-rich carbazole unit is observed by scanning tunneling microscopy (STM) at the highly oriented pyrolytic graphite (HOPG)|solution interface. It is shown that two-dimensional crystals of supramolecular (co)polymers are formed by chain growth polymerization, which in turn can be described by copolymerization statistics. From concentration-dependent measurements, derived copolymerization parameters and DFT calculations, a mechanism for self-assembly is developed that suggests a kinetically driven polymerization process in combination with thermodynamically controlled crystallization.
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