Facet-Selective Dissociation and Radical-Mediated Reaction of Dibenzotetrathiafulvalene Molecules on Low-Index Copper Surfaces

Catalytic bond cleavage and formation of transient intermediates on metal substrates play an essential role in surface synthesis and heterogeneous catalysis. Previous studies usually focus on the bond-breaking process, whereas the knowledge regarding the construction of dissociative moieties that lead to the final products is limited. Here, we investigate the facet-selective dissociation of dibenzotetrathiafulvalene (DBTTF) molecules on Cu(110) and Cu(100) surfaces using low-temperature scanning tunneling microscopy and first-principles calculations. Atomic resolution images enable the identification of various intermediates and reaction pathways on different facets. The dissociation of DBTTF molecules generated 1,2-BDT–Cu complex chains on Cu(110), while phenyl diradical superstructure islands were observed on Cu(100). The various chemical species found on different Cu facets were explained in the context of their formation energies related to the spatial inhomogeneity of surface electronic states. Our results address the effects of electronic and geometrical diversities on the surface mobility of intermediate products and subsequent on-surface reaction pathways.