Luminescent MTN-Type Cluster–Organic Framework with 2.6 nm Cages

From a basic tetrahedral Cu4I4 cluster, a new MTN-type cluster–organic framework (COZ-1) containing giant 64512 and 512 cages was successfully constructed. The 64512 cage has an inner diameter of 2.6 nm and a large pore volume of 9.2 nm3; these tetrahedral Cu4I4 clusters with bulky size offer new opportunities for not only the formation of 4-connected zeotype structures but also the integration of porosity and photoluminescent properties from both the cluster and the framework.