Stepwise Assembly of a Multicomponent Heterometallic Metal–Organic Framework via Th6‑Based Metalloligands

Herein we present a new metalloligand, Th6L12 [IHEP-10; L = 4-pyrazolecarboxylic acid (H2PyC)], which can be used to generate a novel multicomponent heterometallic metal–organic framework (MOF), [[Cu3(μ3-OH)­(NO3)­(H2O)2]2Th6(μ3-O)4(μ3-OH)4(PyC)6(HPyC)6(H2O)6]­(NO3)2 (IHEP-11), through further assembly with second [Cu3(μ3-OH)­(PyC)3] clusters. In IHEP-11, six Cu3 clusters are connected by six NO3 – anions to form an unprecedented annular Cu18 cluster, which can be viewed as a 12-connected node to link with 12 Th6 clusters, resulting a 4,12-connected shp net. Benefiting from the cationic framework and 3D porous structure, IHEP-11 can efficiently remove ReO4 – (an analogue of radioactive 99TcO4 –) from aqueous solution in a wide pH range. This work highlights the feasibility of constructing multicomponent MOFs through a step-by-step synthesis strategy based on metalloligands.