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The synthesis and structure of a giant 102‐silver‐atom nanocluster (NC) 1 is presented. X‐ray structural analysis reveals that 1 features a multi‐shelled metallic core of Ag6@Ag24@Ag60@Ag12. An octahedral Ag6 core is encaged by a truncated octahedral Ag24 shell. The Ag24 shell is composed of a hitherto unknown sodalite‐type silver orthophosphate cluster (SOC) {(Ag3PO4)8}, reminiscent of the Ag3PO4 photocatalyst. The SOC is capped by six interstitial sulfur atoms, giving a unique anionic cluster [Ag6@{(Ag3PO4)8}S6]6−, which functions as an intricate polyhedral template with abundant surface O and S atoms guiding the formation of a rare rhombicosidodecahedral Ag60 shell. An array of 6 linear Ag2 staples further surround this Ag60 shell. [Ag6@{(Ag3PO4)8}S6]6− is an unusual Ag‐based templating anion to induce the assembly of a SOC within silver NC. This finding provides molecular models for bulk Ag3PO4, and offers a fresh template strategy for the synthesis of silver NCs with high symmetry.

New-type protecting ligands beyond the conventional ones are beginning to be introduced in stabilizing new silver NCs.

ILs with reversible construction of ionic networks, which mainly consist of cooperative hydrogen bonds (CHBs) were designed for sigmoidal ammonia (NH3) absorption isotherm, which leads to efficient absorption, energy-saving desorption, and high reversibility. Combined with NH3 absorption–desorption experiments, spectroscopic investigations, NH3–TPD measurement, and quantum-chemical calculations, NH3 absorption mechanism was proposed as the hydrogen bond interaction with IL by overcoming the heat for disorganizing ionic networks, including CHBs breakage and the phase change of IL from solid to liquid. Reversely, the NH3 desorption would be promoted by the heat release for the reformation of ionic networks. Thereinto, [BzAm]­[Tf2N] with ionic networks showed NH3 absorption with threshold pressure at 0.28 bar and NH3 capacity of 2.8 mol NH3/mol IL at 1 bar as well as be desorpted completely just through pressure swing, calorimetric test indicated the exothermic reformation of ionic networks provided 31.8% of energy for NH3 desorption from [BzAm]­[Tf2N]. Furthermore, the ammonia capacity as well as the threshold pressure would be changed by varying the CHBs interaction in IL, that [2PyH]­[Tf2N] with weaker interaction of CHBs indicating decreased threshold pressure at 0.04 bar and enhanced NH3 capacity of 3.8 mol NH3/mol IL at 1 bar. We believe this highly efficient and reversible process by reversible construction of absorbents can provide a potential alternative for NH3 as well as other gas absorption.