The precise introduction of nonplanar pores in the backbone of graphene nanoribbon represents a great challenge. Here, we explore a synthetic strategy toward the preparation of nonplanar porous graphene nanoribbon from a predesigned dibromohexabenzotetracene monomer bearing four cove-edges. Successive thermal annealing steps of the monomers indicate that the dehalogenative aryl-aryl homocoupling yields a twisted polymer precursor on a gold surface and the subsequent cyclodehydrogenation leads to a defective porous graphene nanoribbon containing nonplanar [14]annulene pores and five-membered rings as characterized by scanning tunneling microscopy and noncontact atomic force microscopy. Although the C–C bonds producing [14] annulene pores are not achieved with high yield, our results provide new synthetic perspectives for the on-surface growth of nonplanar porous graphene nanoribbons.

Curved graphene nanoribbons (GNRs) with hybrid edge structures have recently attracted increasing attention due to their unique band structures and electronic properties as a result of their nonplanar conformation. This work reports the solution synthesis of a long and curved multi-edged GNR (cMGNR) with unprecedented cove–armchair–gulf edge structures. The synthesis involves an efficient A2B2-type Diels–Alder polymerization between a diethynyl-substituted prefused bichrysene monomer (3b) and a dicyclopenta[e,l]pyrene-5,11-dione derivative (6) followed by FeCl3-mediated Scholl oxidative cyclodehydrogenation of the obtained polyarylenes (P1). Model compounds 1a and 1b are first synthesized to examine the suitability and efficiency of the corresponding polymers for the Scholl reaction. The successful formation of cMGNR from polymer P1 bearing prefused bichrysene units is confirmed by FTIR, Raman, and solid-state NMR analyses. The cove-edge structure of the cMGNR imparts the ribbon with a unique nonplanar conformation as revealed by density functional theory (DFT) simulation, which effectively enhances its dispersibility in solution. The cMGNR has a narrow optical bandgap of 1.61 eV, as estimated from the UV–vis absorption spectrum, which is among the family of low-bandgap solution-synthesized GNRs. Moreover, the cMGNR exhibits a carrier mobility of ≈2 cm2 V−1 s−1 inferred from contact-free terahertz spectroscopy.