A comparative study of [Ag11(iPrS)9(dppb)3]2+ and [Ag15S(sBuS)12(dppb)3]+: templating effect on structure and photoluminescence

Abstract

Atomically precise silver clusters with tunable photoluminescence (PL) properties have attracted extensive attention due to their great value for basic science and future applications. Here, we report that the addition of a sulfido template into a triangular thiolated silver cluster [Ag₁₁(ⁱPrS)₉(dppb)₃]·2CF₃SO₃·CH₃OH (Ag₁₁, dppb = 1,4-bis(diphenylphosphino)butane), which is emissive at 660 nm under ambient conditions, produced another silver cluster [S@Ag₁₅(^sBuS)₁₂(dppb)₃]·CF₃SO₃·H₂O (Ag₁₅) that displays 716 nm emission with a 56 nm redshift aided by the ligand sec-butyl mercaptan. The sulfido template, which affects the geometrical and electronic structures, results in a redshift of Ag₁₁ room-temperature PL as a result of opening up the template-to-metal charge transfer (TMCT) and disturbing the electronic transition between the metal core and ligands at the periphery.