On-Surface Synthesis of Porous Carbon Nanoribbons from Polymer Chains

• Published in: Journal of the American Chemical Society 2017-09, Vol.139 (37), p.12976-12984
• Main Authors: Ammon, Maximilian, Sander, Tim, Maier, Sabine
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.7b04783

We demonstrate the on-surface synthesis of porous carbon nanoribbons on Ag(111) via a preprogrammed isomerization of conformationally flexible polymer chains followed by dehydrogenation reactions using thermal annealing. The carbon chains are fabricated by polymerization of prochiral 1,3,5-tris­(3-bromophenyl)­benzene (mTBPB) directly on the surface using an Ullmann-type reaction. At room temperature, mTBPB partially self-assembles in halogen-bonded 2D networks, which transform into organometallic chains and rings after debromination. The chain and ring formation is facilitated by conformational switching from a C 3h to Cs symmetry of mTBPB via rotation of m-phenylene units. The high conformational selectivity toward C s -conformers is templated by the twofold coordination to Ag adatoms. After thermally induced covalent-linking through aryl–aryl coupling, well-ordered nanoporous chains are created. Finally, the rotation of single phenylene units in combination with dehydrogenation cross-linking reactions within the polymer chains leads to the unexpected formation of porous carbon nanoribbons. We unveil the reaction mechanism in a low-temperature scanning tunneling microscopy study and demonstrate that the rotation of m-phenylene units is a powerful design tool to promote structural control in the synthesis of cyclic covalent organic nanostructures on metal surfaces.