Here, we report two (AgI3I)4L4 metal-organic cages that each contain a previously unobserved trisilver(I) iodide cluster at their vertices. Clusters containing fewer than 10 AgI 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.
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