Issue 21, 2021

How to not build a cage: endohedral functionalization of polyoxometalate-based metal–organic polyhedra

Abstract

Introducing functionalities into the interior of metal–organic cage complexes can confer properties and utilities (e.g. catalysis, separation, drug delivery, and guest recognition) that are distinct from those of unfunctionalized cages. Endohedral functionalization of such cage molecules, for decades, has largely relied on modifying their organic linkers to covalently append targeted functional groups to the interior surface. We herein introduce an effective coordination method to bring in functionalities at the metal sites instead, for a set of polyhedral cages where the nodes are in situ formed polyoxovanadate clusters, [VIV6O6(OCH3)96-SO4)(COO)3]2−. Replacing the central sulfates of these hexavanadate clusters with more strongly coordinating phosphonate groups allows the installation of functionalities within the cage cavities. Organophosphonates with phenyl, biphenyl, and terphenyl tails were examined for internalization. Depending on the size/shape of the cavities, small phosphonates can fit into the molecular containers whereas larger ones inhibit or transform the framework architecture, whereby the first non-cage complex was isolated from a reaction that otherwise would lead to entropically favored regular polyhedra cages. The results highlight the complex and dynamic nature of the self-assembly process involving polyoxometalates and the scope of molecular variety accessible by the introduction of endo functional groups.

Graphical abstract: How to not build a cage: endohedral functionalization of polyoxometalate-based metal–organic polyhedra

Supplementary files

Article information

Article type
Edge Article
Submitted
02 mar 2021
Accepted
02 apr 2021
First published
03 apr 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2021,12, 7361-7368

How to not build a cage: endohedral functionalization of polyoxometalate-based metal–organic polyhedra

J. Guo, Q. Chang, Z. Liu, Y. Wang, C. Liu, M. Wang, D. Huang, G. Chen, H. Zhao, W. Wang and X. Fang, Chem. Sci., 2021, 12, 7361 DOI: 10.1039/D1SC01243F

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