Recent advancements in on-surface synthesis have enabled the reliable and predictable preparation of atomically precise low-dimensional materials with remarkable properties, which are often unattainable through traditional wet chemistry. Among these materials, porphyrins stand out as a particularly intriguing class of molecules, extensively studied both in solution and on surfaces. Their appeal lies in the ability to fine-tune their unique chemical and physical properties through central metal exchange or peripheral functionalization. However, the synthesis of π-extended porphyrins featuring unsubstituted anthracenyl groups has remained elusive. Herein, we report an in vacuo temperature-controlled cyclodehydrogenation of bis- and tetraanthracenyl Zn(II) porphyrins on a gold(111) surface. By gradually increasing the temperature, sequential dehydrogenation leads to the formation of fused anthracenyl porphyrin products. Notably, at high molecular coverage, the formation of bowl-shaped porphyrins occurs, along with transmetalation of Zn with Au. These findings open the door to a variety of π-extended anthracenyl-containing porphyrin products via cyclodehydrogenation and transmetalation, offering significant potential in the fields of molecular (photo/electro)catalysis, (opto)electronics, and spintronics.

Department of Chemistry University of Zürich 8057 Zürich Switzerland

Molecular Surface Science Group Empa 8600 Dübendorf Switzerland

Nanosurf Laboratory Institute of Physics The Czech Academy of Sciences 16200 Prague Czech Republic

Université Paris Saclay CEA CNRS NIMBE LICSEN 91191 Gif sur Yvette France

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