Structural, chemical, and extrinsic modifications of graphene-based nanostructures enable bandgap tuning, optoelectronics, spintronics, and quantum materials design. A well-known approach to modify their electronic properties involves introducing nonbenzenoid ring topologies in their ideal sp2-hybridized hexagonal lattice, such as azulene or Stone-Wales (SW) defects. However, despite the unique structural and electronic characteristics that these nonalternant defects induce, their systematic incorporation in graphene-based nanostructures remains challenging. Here, we demonstrate the on-surface synthesis of one-dimensional SW-based polymers linked through cumulene bonds on the Au(111) surface via thermal and visible-light-induced reactions of a tailored molecular precursor. Scanning tunneling and noncontact atomic force microscopies reveal the nonplanar structure of SW-based units within the polymer chain, while the chemical structure of the polymer has been verified by Raman spectroscopy in combination with theoretical modeling. Additionally, scanning tunneling spectroscopy measurements show an experimental bandgap of 1.8 eV, which significantly differs from its isostructural cumulene-bridged bisanthene analogs. Our results highlight the critical role of SW defects in the structural and electronic properties of carbon-based conjugated polymers, advancing their design with prospects in next-generation optoelectronic devices.

Center for Advancing Electronics Dresden and Faculty of Chemistry and Food Chemistry Technische Universität Dresden D 01069 Dresden Germany

College of Materials Science and Optoelectronic Technology and Center of Materials Science and Optoelectronics Engineering University of Chinese Academy of Science Beijing 100049 P R China

Departamento de Química Orgánica Facultad de Ciencias Universidad de Granada Unidad de Excelencia en Química Granada 18071 Spain

Department of Information Technology and Electrical Engineering ETH Zurich Zurich 8092 Switzerland

Empa Swiss Federal Laboratories for Materials Science and Technology Überlandstrasse 129 Dübendorf 8600 Switzerland

IMDEA Nanoscience C Faraday 9 Campus de Cantoblanco Madrid 28049 Spain

Institute of Physics of the Czech Academy of Science Cukrovarnická 10 Praha 162 00 Czech Republic

Instituto de Ciencia de Materiales de Madrid CSIC Cantoblanco Madrid 28049 Spain

Max Planck Institute of Microstructure Physics Weinberg 2 06120 Halle Germany

Quantum Center ETH Zürich Zürich 8093 Switzerland

Unidad de Nanomateriales avanzados Imdea Nanoscience Unidad asociada al CSIC por el ICMM Madrid 28049 Spain

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