Organic cage supported metal nanoparticles for applications

Sharma, Vivekanand; Bharadwaj, Parimal K.

doi:10.1039/d0dt02998j

Cited by 10 publications

(5 citation statements)

References 68 publications

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“…Crafting a macrobicyclic cage (MBC) having more than one binding site is indeed important for encapsulating different multifunctional molecules with enhanced efficacy . In some recent literatures, this heterotopicity of macrobicycles has contributed some highlighting efforts in selective catalysis .…”

Section: Resultsmentioning

confidence: 99%

Heteroditopic Macrobicyclic Molecular Vessels for Single Step Aerial Oxidative Transformation of Primary Alcohol Appended Cross Azobenzenes

Sarkar

Ghosh

2021

J. Org. Chem.

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A series of oxy-ether tris-amino heteroditopic macrobicycles (L1–L4) with various cavity dimensions have been synthesized and explored for their Cu(II) catalyzed selective single step aerial oxidative cross-coupling of primary alcohol based anilines with several aromatic amines toward the formation of primary alcohol appended cross azobenzenes (POCABs). The beauty of this transformation is that the easily oxidizable benzyl/primary alcohol group remains unhampered during the course of this oxidation due to the protective oxy-ether pocket of this series of macrobicyclic vessels. Various dimensionalities of the molecular vessels have shown specific size complementary selection for substrates toward efficient syntheses of regioselective POCAB products. To establish the requirement of the three-dimensional cavity based additives, a particular catalytic reaction has been examined in the presence of macrobicycles (L2 and L3) versus macrocycles (MC1 and MC2) and tripodal acyclic (AC1 and AC2) analogous components, respectively. Subsequently, L1–L4 have been extensively utilized toward the syntheses of as many as 44 POCABs and are characterized by different spectroscopic techniques and single crystal X-ray diffraction studies.

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Section: Resultsmentioning

confidence: 99%

Heteroditopic Macrobicyclic Molecular Vessels for Single Step Aerial Oxidative Transformation of Primary Alcohol Appended Cross Azobenzenes

Sarkar

Ghosh

2021

J. Org. Chem.

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“…Several authors have used cages to anchor nanoparticles in the internal cage and to obtain nanoparticles with a controlled narrow size distribution . For instance, Dong, Chen, and co-workers employed 2-hydroxy-1,3,5-triformylbenzene 200 and 1,2-cyclohexanediamine to prepare cage 201 , which was loaded with Ag nanoparticles.…”

Section: Cages and Containers Soluble In Organic Solvents And Their A...mentioning

confidence: 99%

“…Several authors have used cages to anchor nanoparticles in the internal cage and to obtain nanoparticles with a controlled narrow size distribution. 151 For instance, Dong, Chen, and coworkers employed 2-hydroxy-1,3,5-triformylbenzene 200 and 1,2-cyclohexanediamine to prepare cage 201, which was loaded with Ag nanoparticles. This cage has the core structure of cage CC3 89 but changed the 1,3,5-triformylbenzene building block used to prepare cage CC3 by 2-hydroxy-1,3,5-triformylbenzene 200.…”

Section: Capsules and Cagesmentioning

confidence: 99%

Purely Covalent Molecular Cages and Containers for Guest Encapsulation

et al. 2022

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Cage compounds offer unique binding pockets similar to enzyme-binding sites, which can be customized in terms of size, shape, and functional groups to point toward the cavity and many other parameters. Different synthetic strategies have been developed to create a toolkit of methods that allow preparing tailor-made organic cages for a number of distinct applications, such as gas separation, molecular recognition, molecular encapsulation, hosts for catalysis, etc. These examples show the versatility and high selectivity that can be achieved using cages, which is impossible by employing other molecular systems. This review explores the progress made in the field of fully organic molecular cages and containers by focusing on the properties of the cavity and their application to encapsulate guests.

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“…[ 3 ] Recently, the size, dispersion and electronic structure of various noble metal nanoparticles (Pd, Pt, Au, and Rh) have been regulated by covalent bonded organic cage discrete molecules. [ 4 ] The as‐prepared composites of metal nanoparticles and POC (MNP@POC) were found to be good candidates of catalyst in various liquid‐phase reactions in the presence of gas, such as hydrogen generation, [ 5 ] nitroarene reduction [ 6 ] and organic dye decomposition, [ 7 ] Suzuki‐Miyaura coupling, [ 8 ] electrochemical CO 2 reduction, [ 9 ] and semi‐hydrogenation of phenylacetylene. [ 10 ] The last reaction, specifically selective hydrogenation of phenylacetylene to styrene, is urgently needed in industry.…”

Section: Introductionmentioning

confidence: 99%

Isomorphous Substitution of Organic Cage Crystal by Pd Nanoclusters for Selective Hydrogenation

Zhang,

He,

Wang

et al. 2023

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For supporting active metal, the cavity confinement and mass transfer facilitation lie not in one sack, a trade‐off between high activity and good stability of the catalyst is present. Porous organic cages (POCs) are expected to break the trade‐off when metal particles are properly loaded. Herein, three organic cages (CC3, RCC3, and FT‐RCC3) are employed to support Pd nanoclusters for catalytic hydrogenation. Subnanometer Pd clusters locate differently in different cage frameworks by using the same reverse double‐solvents approach. Compared with those encapsulated in the intrinsic cavity of RCC3 and anchored on the outer surface of CC3, the Pd nanoclusters orderly assembled in FT‐RCC3 crystal via isomorphous substitution exhibit superior activity, high selectivity, and good stability for semi‐hydrogenation of phenylacetylene. Isomorphous substitution of FT‐RCC3 crystal by Pd nanoclusters is originated from high crystallization capacity of FT‐RCC3 and specific interaction of each Pd nanocluster with four cage windows. Both confinement function and H2 accumulation capacity of FT‐RCC3 are fully utilized to support active Pd nanoclusters for efficient selective hydrogenation. The present results provide a new perspective to the heterogeneous catalysis field in terms of crystalizing metal nanoclusters in POC framework and outside the cage for making the best use of both parts.

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Organic cage supported metal nanoparticles for applications

Abstract: Porous shape-persistent organic cages can anchor metal nanoparticles either inside the cavity or in the external cavity generated through self-assembly. The size of these nanoparticles range within 1-2 nm depending...

Cited by 10 publications

References 68 publications

Heteroditopic Macrobicyclic Molecular Vessels for Single Step Aerial Oxidative Transformation of Primary Alcohol Appended Cross Azobenzenes

Heteroditopic Macrobicyclic Molecular Vessels for Single Step Aerial Oxidative Transformation of Primary Alcohol Appended Cross Azobenzenes

Purely Covalent Molecular Cages and Containers for Guest Encapsulation

Isomorphous Substitution of Organic Cage Crystal by Pd Nanoclusters for Selective Hydrogenation

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