Highly Efficient Cooperative Catalysis by Co<sup>III</sup>(Porphyrin) Pairs in Interpenetrating Metal–Organic Frameworks

Lin, Zheng‐Zhe; Zhang, Zhi‐Ming; Chen, Yu‐Sheng; Lin, Wenbin

doi:10.1002/anie.201605802

Cited by 85 publications

(60 citation statements)

References 90 publications

(4 reference statements)

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“…[9] AlthoughM OFs with periodically dispersed isolated or adjacent activec atalytic sites as single-site or cooperative catalysts have been explored, precise assembly of multiple active sites into MOF-based catalysts to work synergistically and achieve tandem or cooperative catalysis without isolation of intermediates is still an important challenge. [10][11][12] To address this problem, metal clusters have been introduced into MOFs to develop an ideal multinuclear platform to investigate synergistic interactions with substrates duringc atalytic process. [13,14] These MOFs based on metal clusters (MCOFs) not only break through the geometrical and coordination limits of classical mononuclear complexes to show intriguing architectures and network topologies, but also usually have some unprecedented properties compared to MOFs constructed from single metal ions as nodes, such as magnetism, luminescence, and porous absorption.…”

Section: Introductionmentioning

confidence: 99%

Co‐Cluster‐Based Metal–Organic Frameworks as Selective Catalysts for Benzene Tandem Acylation–Nazarov Cyclization to Benzocyclopentanone

Liu

Gao

Fan

et al. 2017

Chemistry A European J

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One-step selective benzene acylation-Nazarov cyclization is an attractive, yet challenging method for the synthesis of the benzocyclopentanone skeleton, which is key intermediate of many natural products. Herein, two metal-cluster-based metal-organic frameworks (MCOFs) {(H O) [Co (pbcd) (μ -OH) ]⋅CH CH OH⋅4 H O} (1; pbcd=9,9'-(propan-1,3-diyl)bis(9H-carbazole-3,6-dicarboxylic acid) and {[Co (mcd) (HCO )(μ -O) (μ -OH) (H O) ]⋅6 H O⋅5 DMF} (2; mcd=9,9'-methylenebis(9H-carbazole-3,6-dicarboxylic acid) were developed to catalyze a tandem Nazarov cyclization reaction of 1,3-dimethoxybenzene with α,β-unsaturated carboxylic acids for the synthesis of cyclopentenone[b]benzenes. MCOFs 1 and 2, which were constructed from tetranuclear Co cluster [Co (μ -OH) ] and hexanuclear Co cluster [Co (HCO )(μ -O)(μ -OH)], respectively, exhibit high catalytic activity arising not only from their suitable channel size and accessible catalytic sites, but also because of their high density of Lewis acidic sites within the frameworks and the synergic activity among Co ions. In contrast, {[Co (pbcd)(bpe)]⋅2 H O⋅2 DMF} (3; bpe=1,2-bis(pyridin-4-yl)ethane) containing binuclear Co and having large pore windows is a highly selective catalyst for obtaining exclusively the acylation products. Easy product separation, simple reaction procedures, and catalyst recycling make the catalyst system attractive. This work highlights the synergistic effect among ions of MCOFs in interacting with substrates in a sequential or cooperative manner to achieve tandem catalysis.

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Section: Introductionmentioning

confidence: 99%

Co‐Cluster‐Based Metal–Organic Frameworks as Selective Catalysts for Benzene Tandem Acylation–Nazarov Cyclization to Benzocyclopentanone

Liu

Gao

Fan

et al. 2017

Chemistry A European J

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“…[14] Them odularity that comes with MOFs stems from the expansive list of metal centers/clusters and organic ligands.B yj udiciously selecting the building blocks,amicroenvironment is created to aid the targeted catalytic process such as the aforementioned cycloaddition of CO 2 with epoxides. [14] Them odularity that comes with MOFs stems from the expansive list of metal centers/clusters and organic ligands.B yj udiciously selecting the building blocks,amicroenvironment is created to aid the targeted catalytic process such as the aforementioned cycloaddition of CO 2 with epoxides.…”

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confidence: 99%

Lower Activation Energy for Catalytic Reactions through Host–Guest Cooperation within Metal–Organic Frameworks

et al. 2018

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Industrial synthesis is driven by a delicate balance of the value of the product against the cost of production. Catalysts are often employed to ensure product turnover is economically favorable by ensuring energy use is minimized. One method, which is gaining attention, involves cooperative catalytic systems. By inserting a flexible polymer into a metal-organic framework (MOF) host, the advantages of both components work synergistically to create a composite that efficiently fixes carbon dioxide to transform various epoxides into cyclic carbonates. The resulting material retains high yields under mild conditions with full reusability. By quantitatively studying the kinetic rates, the activation energy was calculated, for a physical mixture of the catalyst components to be about 50 % higher than that of the composite. Through the unification of two catalytically active components, a new opportunity opens up for the development of synergistic systems in multiple applications.

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“…Highly ordered structures, such as metal–organic frameworks, have been exploited in this direction as scaffolds to support photoactive molecules in a biomimetic approach . However, even if the photo‐oxidation process itself is as environmentally friendly as possible, a major drawback of these catalysts active sites or structural scaffolds rely on heavy metal atoms . These undesirable components represent an environmental hazard and, therefore, development of biodegradable supported catalysts is of paramount importance.…”

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confidence: 99%

Phthalocyanine–Virus Nanofibers as Heterogeneous Catalysts for Continuous‐Flow Photo‐Oxidation Processes

et al. 2019

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The generation of highly reactive oxygen species (ROS) at room temperature for application in organic synthesis and wastewater treatment represents a great challenge of the current chemical industry. In fact, the development of biodegradable scaffolds to support ROS‐generating active sites is an important prerequisite for the production of environmentally benign catalysts. Herein, the electrostatic cocrystallization of a cationic phthalocyanine (Pc) and negatively charged tobacco mosaic virus (TMV) is described, together with the capacity of the resulting crystals to photogenerate ROS. To this end, a novel peripherally crowded zinc Pc (1) is synthesized. With 16 positive charges, this photosensitizer shows no aqueous aggregation, and is able to act as a molecular glue in the unidimensional assembly of TMV. A step‐wise decrease of ionic strength in mixtures of both components results in exceptionally long fibers, constituted by hexagonally bundled viruses thoroughly characterized by electron and confocal microscopy. The fibers are able to produce ROS in a proof‐of‐concept microfluidic device, where they are immobilized and irradiated in several cycles, showing a resilient performance. The bottom‐up approach also enables the light‐triggered disassembly of fibers after use. This work represents an important example of a biohybrid material with projected application in light‐mediated heterogeneous catalysis.

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Highly Efficient Cooperative Catalysis by Co^III(Porphyrin) Pairs in Interpenetrating Metal–Organic Frameworks

Cited by 85 publications

References 90 publications

Co‐Cluster‐Based Metal–Organic Frameworks as Selective Catalysts for Benzene Tandem Acylation–Nazarov Cyclization to Benzocyclopentanone

Co‐Cluster‐Based Metal–Organic Frameworks as Selective Catalysts for Benzene Tandem Acylation–Nazarov Cyclization to Benzocyclopentanone

Lower Activation Energy for Catalytic Reactions through Host–Guest Cooperation within Metal–Organic Frameworks

Phthalocyanine–Virus Nanofibers as Heterogeneous Catalysts for Continuous‐Flow Photo‐Oxidation Processes

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Highly Efficient Cooperative Catalysis by CoIII(Porphyrin) Pairs in Interpenetrating Metal–Organic Frameworks

Cited by 85 publications

References 90 publications

Co‐Cluster‐Based Metal–Organic Frameworks as Selective Catalysts for Benzene Tandem Acylation–Nazarov Cyclization to Benzocyclopentanone

Co‐Cluster‐Based Metal–Organic Frameworks as Selective Catalysts for Benzene Tandem Acylation–Nazarov Cyclization to Benzocyclopentanone

Lower Activation Energy for Catalytic Reactions through Host–Guest Cooperation within Metal–Organic Frameworks

Phthalocyanine–Virus Nanofibers as Heterogeneous Catalysts for Continuous‐Flow Photo‐Oxidation Processes

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Highly Efficient Cooperative Catalysis by Co^III(Porphyrin) Pairs in Interpenetrating Metal–Organic Frameworks