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. 2025 Jan 2;64(1):e202412978.
doi: 10.1002/anie.202412978. Epub 2024 Oct 29.

Solution Versus On-Surface Synthesis of Peripherally Oxygen-Annulated Porphyrins through C-O Bond Formation

Joel Deyerling  1 , Beatrice Berionni Berna  2 , Dmytro Biloborodov  3 , Felix Haag  1 , Sena Tömekce  1 , Marc G Cuxart  1 , Conghui Li  1 , Willi Auwärter  1 , Davide Bonifazi  2
Affiliations

Solution Versus On-Surface Synthesis of Peripherally Oxygen-Annulated Porphyrins through C-O Bond Formation

Joel Deyerling et al. Angew Chem Int Ed Engl. .

Abstract

This study investigates the synthesis of tetra- and octa-O-fused porphyrinoids employing an oxidative O-annulation approach through C-H activation. Despite encountering challenges such as overoxidation and instability in conventional solution protocols, successful synthesis was achieved on Au(111) surfaces under ultra-high vacuum (UHV) conditions. X-ray photoelectron spectroscopy, scanning tunneling microscopy, and non-contact atomic force microscopy elucidated the preferential formation of pyran moieties via C-O bond formation and subsequent self-assembly driven by C-H⋅⋅⋅O interactions. Furthermore, the O-annulation process was found to reduce the HOMO-LUMO gap by lifting the HOMO energy level, with the effect rising upon increasing the number of embedded O-atoms.

Keywords: C−O bond formation; O-annulation; non-contact atomic force microscopy; on-surface synthesis; porphyrin.

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