Creating supramolecular semiregular Archimedean tilings via gas-mediated deprotonation of a terminal alkyne derivative

Combining surface-confined reactions with supramolecular self-assembly allows the chemical transformation of simple molecular precursors into higher-level tectons to generate complex tessellations with unique structural and functional properties. Herein, utilizing low-temperature scanning tunnelling microscopy, we firstly confirm a highly efficient chemical reaction converting ethynyl-phenanthrene (EP) precursors into bis(phenanthren-2-yleythnyl)silver (BPE-Ag) complexes adsorbed on Ag(111)/mica at room temperature via a novel oxygen-gas mediated terminal alkyne deprotonation process. Moreover, we show that the BPE-Ag species engage in the formation of three distinct types of long-range ordered nanoporous supramolecular architectures, which can be tuned by the initial EP coverage. For all three phases, the basic tectons were verified to be BPE-Ag dimers with flexible pairing configurations. Intriguingly, our tiling analysis reveals that two phases belong to the (3.6.3.6) class of semiregular Archimedean tiling (AT) and the third expresses a new (3.4.6.4) AT, different from the previously reported related networks. Our results illustrate the potential of the introduced synthesis strategy towards accessing architectures with increased complexity and pave the way towards further control and exploration regarding functional properties of interfacial semiregular ATs.