Two (AgI3I)4L4 cages elucidate the rules for silver-cluster vertex design

Abstract

Here, we report two (Ag^I₃I)₄L₄ metal-organic cages that each contain a previously unobserved trisilver(I) iodide cluster at their vertices. Clusters containing fewer than 10 Ag^I ions are challenging to synthesize in an atomically precise manner. Previous work has demonstrated the potential of the approach of generating such clusters during the formation of higher-order metal-organic cage superstructures, but too few examples were known for design principles to be deciphered. Through analysis of the set of such cages reported herein and previously, we elaborate a set of design principles for their synthesis.