On-Surface Synthesis and Characterization of Honeycombene Oligophenylene Macrocycles

We report the on-surface formation and characterization of [30]-honeycombene, a cyclotriacontaphenylene, which consists of 30 phenyl rings (C180H120) and has a diameter of 4.0 nm. This shape-persistent, conjugated, and unsubstituted hexagonal hydrocarbon macrocycle was obtained by solvent-free synthesis on a silver (111) single-crystal surface, making solubility enhancing alkyl side groups unnecessary. Side products include strained macrocycles with square, pentagonal, and heptagonal shape. The molecules were characterized by scanning tunneling microscopy and density functional theory (DFT) calculations. On the Ag(111) surface, the macrocycles act as molecular quantum corrals and lead to the confinement of surface-state electrons inside the central cavity. The energy of the confined surface state correlates with the size of the macrocycle and is well described by a particle-in-the-box model. Tunneling spectroscopy suggests conjugation within the planar rings and reveals influences of self-assembly on the electronic structure. While the adsorbed molecules appear to be approximately planar, the free molecules have nonplanar conformation, according to DFT.German Science Foundation (Collaborative Research Center 1083); German Science Foundation [GO 1812/2-1]; National Natural Science Foundation of China [21133001, 21333001, 913000002, 21373020, 21403008, 61321001, 21433011]; Ministry of Science and Technology [2014CB239302, 2013CB933404, 2011CB808702]; Research Fund for the Doctoral Program of Higher Education [20130001110029]; Chinese Academy of Sciences; Cluster of Excellence "Engineering of Advanced Materials" located at the University of Erlangen-NurnbergSCI(E)ARTICLE1134-1431