The confinement effects within coordination cages present powerful tools in modern chemistry, particularly for the synthesis and manipulation of complex molecules. This concept article reviews the use of coordination cages to stabilize and tune the properties of polyoxometalates (POMs), a class of nano-sized metallic clusters, expanding the focus beyond traditional organic reactions. The article provides a brief overview of coordination cages, POM chemistry and discusses the encapsulation of POMs in coordination cages, highlighting how these cages provide a confinement effect that enhances the stability and reactivity of POMs. Additionally, the concept of cavity-directed synthesis is explored as a method for creating labile POMs, which are often unstable in aqueous conditions, underlining its implications for supramolecular catalysis. Future research will focus on expanding the structures and applications of encapsulated POMs, as well as improving cage designs to unlock new cluster architectures.
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http://dx.doi.org/10.1002/chem.202403856 | DOI Listing |
Nat Commun
January 2025
State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, China.
Intensified host-guest electronic interplay within stable metal-organic cages (MOCs) presents great opportunities for applications in stimuli response and photocatalysis. Zr-MOCs represent a type of robust discrete hosts for such a design, but their host-guest chemistry in solution is hampered by the limited solubility. Here, by using pyridinium-derived cationic ligands with tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (BAr) as solubilizing counteranions, we report the preparation of soluble Zr-MOCs of different shapes (1-4) that are otherwise inaccessible through a conventional method.
View Article and Find Full Text PDFSci Bull (Beijing)
December 2024
Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China. Electronic address:
Tailored design of organic linkers or metal nodes can introduce desirable functionalities into metal-organic cages (MOCs), significantly expanding their potential applications. In this study, we present a viable approach for engineering acyl-type metal nodes to create interior oxygen-rich sites within MOCs, enabling specific recognition of metal ions, including radioactive contaminants, while maintaining the structural integrity of the MOCs. A novel MOC featuring a uranyl-sealed calix[4]resorcinarene (C[4]R)-based multisite cavity, referred to as UOC, is synthesized as a prototype.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Department of Chemistry, Indiana University, Bloomington, Indiana 47405, USA.
This manuscript explores the post-synthetic modification (PSM) of amine-functionalized porous coordination cages, specifically focusing on the formation of imine bonds through reactions with aldehydes. Targeting various cage topologies, including zirconium-, magnesium-, and molybdenum-based structures, we demonstrate the tunability of cage solubility and porosity through selective functionalization where the proximity of amine groups on the parent cage impacts the extent of modification. The work highlights the reversible nature of imine formation, offering potential applications in solubility switching and mixed-metal solid synthesis.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, National & Local United Engineering Laboratory for Power Battery Institution, Northeast Normal University, Changchun, Jilin, 130024, China.
Construction of metal-organic cages (MOCs) with internal modifications is a promising avenue to build enzyme-like cavities and unlocking the mystery of highly catalytic activity and selectivity of enzymes. However, current interests are mainly focused on single-metal-node cages, little achievement has been expended to metallocluster-based architectures, and the in situ endogenous generation of metal clusters. Herein, based on the hard-soft-acids-bases (HSAB), the metallocluster-based heterometallic MOC (CuVMOP) constructed of [CuOPz] and [VO(OCH)(SO)(CO)] clusters was obtained by one-pot method.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
State Key Laboratory of Chemo/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, 410082, Changsha, Hunan, China.
Electrocatalytic synthesis of high-value chemicals has been attracting growing interest owing to its environmentally benign reaction pathways. Among these processes, the electrocatalytic reduction of nitrate (NO ) to ammonia (NH), known as NORR, and the oxidation of 5-hydroxymethylfurfural (HMFOR) stand out as two cornerstone reactions; yet, their efficiency and selectivity pose ongoing challenges. In this study, we introduce a charge manipulation approach for the design of highly efficient electrocatalysts tailored for the simultaneous coupling of NORR and HMFOR.
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