Polyoxometalate-based macrocycles and their assembly

Ma, Xiao-Qi; Xiao, Hui-Ping; Chen, Yi; Lai, Qian-Sheng; Li, Xin-Xiong; Zheng, Shou-Tian

doi:10.1016/j.ccr.2024.215818

“…Polyoxometalates (POMs) are a prominent type of discrete early-transition metal-oxo clusters with a diversity of structures and properties. − In the field of POMs, the synthesis of giant hollow POM cages is interesting and important since they not only have fascinating architectures but also combine the benefits of POM cluster and porous cage; thus, they are highly promising for applications in catalysis, guest recognition, and molecular reactors. − To date, although a number of giant hollow POM cages, e.g., “hedgehog-like” Mo 368 , truncated icosahedral Mo 132 and U 60 , pentagonal dodecahedral Mo 240 , have been successfully explored by chemists, there is still a lack of an effective strategy in the synthesis for guiding researchers to explore more derivatives or homologs. From the synthesis experiences of traditional POMs, molecular growth based on some known POMs seems to be a good idea for constructing more POM derivatives. − In particular, it is even possible to synthesize a series of derivatives that possess identical main skeleton with the pristine parent POMs. − Such POM derivatives not only largely enrich the structures and properties of traditional POMs but also provide a unique platform for studying their structural transformation process as well as the structure–property relationships. − In this context, the construction of a series of isotypic giant POM cages that can maintain the pristine parent structure and large opening cavities by a molecular growth approach is very interesting and important, but reports on this breakthrough have not been found so far.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Isotypic Giant Polymolybdate Cages for Efficient Photocatalytic C–C Coupling Reactions

Lin,

Mei,

Guo

et al. 2024

J. Am. Chem. Soc.

3

0

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The construction of isotypic high-nuclearity inorganic cages with identical pristine parent structure and increasing nuclearity is highly important for molecular growth and structure− property relationship study, yet it still remains a great challenge. Here, we provide an in situ growth approach for successfully synthesizing a series of new giant hollow polymolybdate dodecahedral cages, Mo 250 , Mo 260 -I, and Mo 260 -E, whose structures are growth based on giant polymolybdate cage Mo 240 . Remarkably, they show two pathways of nuclear growth based on Mo 240 , that is, the growth of 10 and 20 Mo centers on the inner and outer surfaces to afford Mo 250 and Mo 260 -I, respectively, and the growth of 10 Mo centers both on the inner and outer surfaces to give Mo 260 -E. To the best of our knowledge, this is the first study to display the internal and external nuclear growth of a giant hollow polyoxometalate cage. More importantly, regular variations in structure and nuclearity confer these polymolybdate cages with different optical properties, oxidative activities, and hydrogen atom transfer effect, thus allowing them to exhibit moderate to excellent photocatalytic performance in oxidative crosscoupling reactions between different unactivated alkanes and N-heteroarenes. In particular, Mo 240 and Mo 260 -E with better comprehensive abilities can offer the desired coupling product with yield up to 92% within 1 h.

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High‐Nuclearity Polyoxometalate‐Based Metal–Organic Frameworks for Photocatalytic Oxidative Cleavage of C−C Bond

Zhao,

Zeng,

Jiang

et al. 2024

Angewandte Chemie

0

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High‐nuclearity polyoxometalate (POM) clusters are attractive building blocks (BBs) for the synthesis of metal‐organic frameworks (MOFs) due to their high connectivity and inherently multiple metal centers as functional sites. This work demonstrates a strategy of step‐wise growth on ring‐shaped [P8W48O184]40‐ precursor, which produced two new high‐nuclearity polyoxotungstates, a half‐closed [H16P8W58O218]32‐ {W58} and a fully‐closed [H16P8W64O236]32‐ {W64}. By in‐situ synthesis, unique MOFs of copper triazole‐benzoic acid (HL) complexes incorporating the negatively‐charged {W58} and {W64} as nodes, {Cu11(HL)8LW58} HNPOMOF‐1 and {Cu9(HL)9W64} HNPOMOF‐2, were constructed by delicately tuning the reaction conditions, mainly solution pH, which controls the formation of {W58} and {W64}, and at the same time the protonation of triazole‐benzoic acid ligand thus its coordination mode to copper ion that creates the highest nuclearity POM‐derived MOFs reported to date. HNPOMOF‐1 features 3D framework possessing cage‐like cavities filled with exposed carboxyl groups, while the inherent 2D layer‐like HNPOMOF‐2 allows for facile exfoliation into ultrathin nanosheets, and the resulted HNPOMOF‐2NS exhibits superior activity towards photocatalytic oxidative cleavage of C‐C bond for a series of lignin models. This work not only provides a strategy to build high‐nuclearity POM cluster‐based frameworks, but also demonstrates their great potential as functional materials for green catalysis.

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High‐Nuclearity Polyoxometalate‐Based Metal–Organic Frameworks for Photocatalytic Oxidative Cleavage of C−C Bond

Zhao,

Zeng,

Jiang

et al. 2024

Angew Chem Int Ed

0

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High‐nuclearity polyoxometalate (POM) clusters are attractive building blocks (BBs) for the synthesis of metal‐organic frameworks (MOFs) due to their high connectivity and inherently multiple metal centers as functional sites. This work demonstrates a strategy of step‐wise growth on ring‐shaped [P8W48O184]40‐ precursor, which produced two new high‐nuclearity polyoxotungstates, a half‐closed [H16P8W58O218]32‐ {W58} and a fully‐closed [H16P8W64O236]32‐ {W64}. By in‐situ synthesis, unique MOFs of copper triazole‐benzoic acid (HL) complexes incorporating the negatively‐charged {W58} and {W64} as nodes, {Cu11(HL)8LW58} HNPOMOF‐1 and {Cu9(HL)9W64} HNPOMOF‐2, were constructed by delicately tuning the reaction conditions, mainly solution pH, which controls the formation of {W58} and {W64}, and at the same time the protonation of triazole‐benzoic acid ligand thus its coordination mode to copper ion that creates the highest nuclearity POM‐derived MOFs reported to date. HNPOMOF‐1 features 3D framework possessing cage‐like cavities filled with exposed carboxyl groups, while the inherent 2D layer‐like HNPOMOF‐2 allows for facile exfoliation into ultrathin nanosheets, and the resulted HNPOMOF‐2NS exhibits superior activity towards photocatalytic oxidative cleavage of C‐C bond for a series of lignin models. This work not only provides a strategy to build high‐nuclearity POM cluster‐based frameworks, but also demonstrates their great potential as functional materials for green catalysis.

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Polyoxometalate-based macrocycles and their assembly

Cited by 6 publications

References 234 publications

Synthesis of Isotypic Giant Polymolybdate Cages for Efficient Photocatalytic C–C Coupling Reactions

Synthesis of Isotypic Giant Polymolybdate Cages for Efficient Photocatalytic C–C Coupling Reactions

High‐Nuclearity Polyoxometalate‐Based Metal–Organic Frameworks for Photocatalytic Oxidative Cleavage of C−C Bond

High‐Nuclearity Polyoxometalate‐Based Metal–Organic Frameworks for Photocatalytic Oxidative Cleavage of C−C Bond

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