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Covalent Postassembly Modification and Water Adsorption of Pd3 Self-Assembled Trinuclear Barrels

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posted on 02.02.2016, 00:00 by Dipak Samanta, Aniket Chowdhury, Partha Sarathi Mukherjee
Three new ditopic imidazole ligands (24) were synthesized in high yields and characterized by various spectroscopic techniques. These ligands resulted in the formation of [3 + 6] self-assembled trinuclear barrels (57) in quantitative yields by stoichiometric combination of individual ligands and Pd­(NO3)2 in DMSO. All the three assemblies (57) were characterized by 1H NMR and ESI-MS analysis, and subsequently, structures of the complexes 5 and 6 were confirmed by single-crystal X-ray diffraction studies. Structure analysis reveals the presence of NO3 counteranions in the intermolecular channels/pockets, which could potentially act as H-bonding sites between adsorbed water molecules within the channels. In fact, both the assemblies (5 and 6) showed water uptake (136.58, and 123.78 cm3 g–1, respectively) at ambient temperature under maximum allowable humidity. In addition, free aldehyde group present in the bridging ligand in complex 7 provides reactive site for postassembly modification. Herein, Knoevenagel condensation with Meldrum’s acid was utilized under mild conditions by targeting aldehyde group appended in prefabricated complex 7 and transformed into a different complex (8) with altered functional group. Such postassembly functionalization enables incorporation of a new functional group without disrupting the integrity of the trifacial structure.