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Flexibility Induced Encapsulation of Ultrafine Palladium Nanoparticles into Organic Cages for Tsuji–Trost Allylation

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journal contribution
posted on 05.02.2020 by Vivekanand Sharma, Dinesh De, Ranajit Saha, Pratim Kumar Chattaraj, Parimal K. Bharadwaj
A series of three positional isomers of organic cages namely o-OC, m-OC, and p-OC, have been self-assembled using dynamic covalent chemistry. Their room temperature controlled fabrication with palladium gives ultrafine diameter (1–2 nm) of palladium nanoparticles (Pd NPs). We observed that the shape-flexibility of cages have great impact on the formation of Pd NPs. Theoretical calculations reveals that theoretically obtainable size of Pd NPs for each cage which was complementary to the experimental results. Theoretical studies indicate that the driving forces for the specific orientational preference may be ascribed to subtle variations on the level of π–π interactions, which ultimately governs the growth of Pd NPs therein. It is the first example of shape-flexible synthesis of organic cages where flexibility governs the nanoparticle growth. Pd NPs have shown excellent catalysis of Tsuji–Trost allylation at room temperature and pressure in water.