A Straightforward Strategy for Constructing Zirconium Metallocavitands

Abstract

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.

Multivariate porous platform based on metal-organic polyhedra with controllable functionality assembly

“…Isoreticular series of Zr-based MOPs After screening previously reported MOPs, we selected the Zr-based MOP as a promising candidate for the multivariate platform. Zr-based MOPs display structural robustness and chemical stability, [36][37][38][39][40][41][42][43][44][45][46][47][48][49] two important advantages for synthesis and further characterization. Based on such features, Zr-based MOPs have become an emerging class of porous solids.…”

Utilization of a Mixed-Ligand Strategy to Tune the Properties of Cuboctahedral Porous Coordination Cages

“…4 Indeed, similar to MOF chemistry, the majority of cages for which surface areas have been reported are based on first or second row transition metal cations and multitopic carboxylate-based organic linkers. 5,6 Among these, bimetallic, 7 trimetallic, 8 and tetrametallic 9 clusters have been widely studied as paddlewheel-based, 10 cyclopentadienecapped, 11 or calixarene-terminated cages, 12 respectively.…”

“…Although coordination cages have been studied for decades, their promise as a new class of permanently porous solid materials has been demonstrated only relatively recently. − As a subset of supramolecular complexes, permanently porous coordination cages that are structurally analogous to many common metal–organic frameworks are often the most widely studied in this regard . Indeed, similar to MOF chemistry, the majority of cages for which surface areas have been reported are based on first or second row transition metal cations and multitopic carboxylate-based organic linkers. , Among these, bimetallic, trimetallic, and tetrametallic clusters have been widely studied as paddlewheel-based, cyclopentadiene-capped, or calixarene-terminated cages, respectively.…”

Molecularly Homogenized Composite Membranes Containing Solvent-Soluble Metallocavitands for CO2/CH4 Separation

“…Metallocavitands, a new emerging class of functional multimetallic complexes with specific cavities, are considered promising materials in many fields, such as sensing, catalysis, light-harvesting, drug delivery, and some biomedical technologies. − In addition to the advantages of the multimetallic complexes mentioned above, the special configuration of metallocavitands can host a series of guest molecules according to the shape or specific weak interactions. , To the best of our knowledge, the study on MMMs with metallocavitands as the filler has not been reported yet.…”