Monitoring two-dimensional coordination reactions: directed assembly of co-terephthalate nanosystems on Au(111).

We report scanning tunneling microscopy observations on the formation of 2D Co-based coordination compounds on the reconstructed Au(111) surface. Preorganized arrays of Co bilayer islands are shown to be local reaction sites, which are consumed in the formation of Co-terephthalate aggregates and regular nanoporous grids. The latter exhibit a planar geometry stabilized by the smooth substrate. The nanogrids are based on a rectangular motif, which is understood as an intrinsic feature of a 2D cobaltous terephthalate sheet and dominates over the templating influence of the quasihexagonal substrate atomic lattice. The dynamics of the Co island dissolution and metallosupramolecular self-assembly could be monitored in situ. Complementary first-principles calculations were performed to analyze the underlying driving forces and to examine general trends in 2D metal-carboxylate formation. The findings indicate the wide applicability of coordination chemistry concepts at surfaces, which moreover can be spatially confined by using templated substrates, and its potential to synthesize arrangements unavailable in bulk materials.