Regiospecific C-H activation is a promising approach to achieve extended polymers with tailored structures. While a recent on-surface synthetic approach has enabled regioselective homocoupling of heteroaromatic molecules, only small oligomers have been achieved. Herein, selective C-H activation for dehydrogenative C-C couplings of hexaazatriphenylene by Scholl reaction is reported for the first time. By combining low-temperature scanning tunneling microscopy (STM) and atomic force microscopy (AFM), we revealed the formation of one-dimensional polymers with a double-chain structure. The details of the growth process are rationalized by density functional theory (DFT) calculations, pointing out a cooperative catalytic action of Na and Ag adatoms in steering the C-H selectivity for the polymerization.

Department of Chemistry and Catalysis Research Center Technical University of Munich 85748 Garching Germany

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

Department of Chemistry Zhejiang Sci Tech University Hangzhou China

Institute of Experimental and Applied Physics University of Regensburg 93053 Regensburg Germany

Institute of Physics of Czech Academy of Sciences 16200 Prague Czech Republic

Regional Centre of Advanced Technologies and Materials Czech Advanced Technology and Research Institute Palacký University Olomouc 78371 Olomouc Czech Republic

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