The 12 S atoms of the intermediate layer were bonded to 12 Ag atoms of Ag42(S t Bu)20 (X@{Ag12S8}S12[Ag42(S t Bu)20]) (highlighted in blue, Figure ). On the surface of X@{Ag12S8}S12[Ag42(S t Bu)20], the S atoms of S( t Bu) were arranged in a regular icosahedral structure with two coordination modes: μ3-S( t Bu) and μ4-S( t Bu) (Figure and). The m SO3 t Bu ligands were coordinated with 12 Ag atoms of Ag42(S t Bu)20 (highlighted in blue, Figure ), which were bonded to the S atoms of the intermediate layer, as well as 2 Ag atoms of remaining Ag30(S t Bu)20 (highlighted in red, Figure ) in the coordination mode of μ3-O3S( t Bu)-κ 3 O,Oʹ,Oʹʹ (Figure ).