Transmetalation in Surface-Confined Single-Layer Organometallic Networks with Alkynyl-Metal-Alkynyl Linkages.

Transmetalation represents an appealing strategy toward fabricating and tuning functional metal-organic polymers and frameworks for diverse applications. In particular, building two-dimensional metal-organic and organometallic networks affords versatile nanoarchitectures of potential interest for nanodevices and quantum technology. The controlled replacement of embedded metal centers holds promise for exploring versatile material varieties by serial modification and different functionalization. Herein, we introduce a protocol for the modification of a single-layer carbon-metal-based organometallic network via transmetalation. By integrating external Cu atoms into the alkynyl-Ag organometallic network constructed with 1,3,5-triethynylbenzene precursors, we successfully realized in situ its highly regular alkynyl-Cu counterpart on the Ag(111) surface. While maintaining a similar lattice periodicity and pore morphology to the original alkynyl-Ag sheet, the Cu-based network exhibits increased thermal stability, guaranteeing improved robustness for practical implementation.