Synthesizing Highly Regular Single-Layer Alkynyl-Silver Networks at the Micrometer Scale via Gas-Mediated Surface Reaction.

Extended organometallic honeycomb alkynyl-silver networks have been synthesized on a noble metal surface under ultrahigh vacuum conditions via a gas-mediated surface reaction protocol. Specifically, the controlled exposure to molecular oxygen efficiently deprotonates terminal alkyne moieties of 1,3,5-tris(4-ethynylphenyl)benzene (Ext-TEB) precursors adsorbed on Ag(111). At Tsub = 200 K, this O2-mediated reaction pathway features high chemoselectivity without poisoning the surface. Through mild annealing to 375 K, long-range ordered alkynyl-silver networks incorporating substrate atoms evolve, featuring Ag- bis-acetylide motifs, high structural quality and a regular arrangement of nanopores with a van der Waals cavity of ≈8.3 nm2.