Studies on supramolecular assemblies, metal complexes of aromatic oxime derivatives for molecular and ions recognition
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Different self-assemblies of oxime derivatives, some of their cocrystals and ionic salts are studied through crystal engineering approach. Properties of oximes as well as their different adducts in solid state are compared with the properties observed in solution. The formation and stability of self-assemblies of hydroxy-aromatic aldoximes with different tetrabutylammonium fluoride salts are essentially guided by the intrinsic acidity of fluoride ions. Different oxime derivatives and transition metal aldoxime complexes showed selectively detect fluoride ions in the presence of other anions. The role of metal ion in the complexes on the recognition process is ascertained. The inclusion of a dihydroxy-aromatic aldoxime in cadmium coordination polymer is compared with corresponding inclusion complex with the parent aldehyde to show the stability of the oxime derivative in confined conditions. Recognition of oxime derivatives by nitrogen containing compounds in solution and solid state are demonstrated. Competition between different types of acid-oxime interactions is investigated and various synthons in the cocrystals are described. Pre-designed non-covalent synthesis and the domain expansions of the sub-assemblies are elucidated. Photophysical and thermal properties of picrate salts of aromatic amine or heterocyclic linked oxime derivatives are studied and a unique example protonation at oxime nitrogen atom by picric acid was identified and their physicochemical properties are established. The thesis has improvised the scope of pre-designed non-covalent synthesis utilizing interplay of the weak interactions of oximes to generate new supramolecular assemblies with interesting optical properties in solid or solution state for molecular and ion recognitions.
Supervisor: Jubaraj B Baruah