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 linear Ag-bis-acetylide motifs, high structural quality and a regular arrangement of nanopores with a van der Waals cavity of ≈ 8.3 nm2