The design of organometallic complexes is at the heart of modern organic chemistry and catalysis. Recently, on-surface synthesis has emerged as a disruptive paradigm to design previously precluded compounds and nanomaterials. Despite these advances, the field of organometallic chemistry on surfaces is still at its infancy. Here, we introduce a protocol to activate the inner diacetylene moieties of a molecular precursor by copper surface adatoms affording the formation of unprecedented organocopper metallacycles on Cu(111). The chemical structure of the resulting complexes is characterized by scanning probe microscopy and X-ray photoelectron spectroscopy, being complemented by density functional theory calculations and scanning probe microscopy simulations. Our results pave avenues to the engineering of organometallic compounds and steer the development of polyyne chemistry on surfaces.

Departamento de Química Orgánica Facultad de Ciencias Químicas Universidad Complutense de Madrid 28040 Madrid Spain

Department of Chemistry Biochemistry and Pharmaceutical Sciences University of Bern 3012 Bern Switzerland

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

IMDEA Nanoscience C Faraday 9 Campus de Cantoblanco 28049 Madrid Spain

Institute of Physics École Polytechnique Fédérale de Lausanne CH 1015 Lausanne Switzerland

Institute of Physics of the Czech Academy of Science 16253 Praha Czech Republic

Istituto di Struttura della Materia CNR via Fosso del Cavaliere 100 00133 Roma Italy

Physics Department E20 Technical University of Munich D 85748 Garching Germany

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