Metallocavitands (MCs), a new burgeoning class of functional multimetallic molecules with specific cavities, are considered as promising materials in many fields. However, designing and constructing metallocavitands with compatibility and tunability from simple ligands is highly challenging. In this work, a series of Zr-based MCs with three distinct structural types have been prepared based on in situ generated trinuclear zirconocene (Cp 3 Zr 3 ) secondary building blocks (SBBs) and Vshaped dicarboxylic linkers. First, a novel window-shaped Zr-based MC, namely ZrMC-1, has been constructed based on four Cp 3 Zr 3 SBBs and six simple isophthalate linkers. Its window size and environment could be easily modified by different functional groups, including nitro (−NO 2 ) and amino (−NH 2 ). Interestingly, the amino-functionalized one, ZrMC-1-NH 2 , can serve as a robust heterogeneous cascade catalyst to effectively catalyze the one-pot tandem deacetalization−Knoevenagel condensation reactions. Second, with the introduction of a sulfonic (−SO 3 H) group, an unprecedented bowel-like Zr-based MC, namely ZrMC-2, comprising three Cp 3 Zr 3 SBBs and four 5-sulfoisophthalate ligands, has been obtained. Unexpectedly, one sulfonic group of the ligand coordinates to the Cp 3 Zr 3 SBB, forming the base of ZrMC-2. Finally, an unexpected zigzag-shaped MC denoted as ZrMC-3 has been prepared by using 2,5-thiophenedicarboxylic acids, featuring a larger bend angle than that of the isophthalate-type one. Specifically, ZrMC-3 contains two Zr-based prisms with three Cp 3 Zr 3 SBBs and four 2,5-thiophenedicarboxylate linkers; the bottoms of these two prisms are bridged by another 2,5-thiophenedicarboxylate linker. These results highly suggest that Cp 3 Zr 3 can be an excellent SBB to construct MCs with fascinating architectures and properties by merely varying the organic linkers.

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Fluorescent agents play an important role in the peroxyoxalate chemiluminescence system. However, the effect of different frameworks on chemiluminescence (CL) has not been explored. Herein two pyrene-based metal–organic frameworks (MOFs), [Pb2L] n ·2nDMA·2nH2O (1) and [(Ca2L)·(DMF)3] n ·2.5nDMF·6nH2O (2) (H4L = 5,5′-(-pyrene-1,6-diyl)-diisophthalic acid; DMA = N,N′-dimethylacetamide; DMF = N,N′-dimethylformamide), have been successfully synthesized and are applied to CL. They both exhibit strong and lasting emission that is visible to the naked eye and is significantly stronger than that of the ligand. More importantly, compared with 2, 1 has notably better CL performance. We infer that the reason may be that 1 has higher stability and larger open channels, which can avoid the aggregation of organic ligands as well as provide an effective pathway for the active substance to diffuse into the channels.