On-Surface Synthesis of Porous Carbon Nanoribbons from Polymer Chains.

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 C3h to Cs symmetry of mTBPB via rotation of m-phenylene units. The high conformational selectivity toward Cs-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.