Synthesis of Chalcogen Containing Compounds and Study of Their Sensing and Complexation Property

Dutta, Pradip Kumar (2013) Synthesis of Chalcogen Containing Compounds and Study of Their Sensing and Complexation Property. PhD thesis, Indian Institute of Science Education & Research Kolkata.

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Abstract

This thesis deals with the synthesis and characterization of new ligands comprising group-16 element, mainly, sulfur and selenium derivatives and their complexation properties. Chapter 1 deals with the general introduction based on recent literatures. Chapter 2 deals with the synthesis of some azomethine diselenides and their supramolecular property. Azomethine diselenides were synthesized by condensation of bis(o-formylphenyl) diselenide with aniline, p-bromoaniline, benzylamine, ethanolamine and 1-aminopropanol, respectively. Supramolecular properties of these compounds have been studied by X-ray crystallography and thermal gravimetric analysis (TGA). Chapter 3 comprises the synthesis of bis(methyl)thiasalen ligand, its oxygen analogue and their complexation property towards Pd(II) and Pt(II). The complexation of bis(methyl)thiasalen ligand with Pd(II) afforded two complexes depending on the reaction time. Shorter reaction time (5 min) afforded thioether complex whereas with increase in reaction time (4 h) thioether-thiolate complex was obtained via cleavage of one of the two S–C(Me) bonds of bis(methyl)thiasalen podand upon complexation. The reaction of the same ligand with Pt(II) afforded only thiolate-thioether complex independent of the reaction time. Chapter 4 includes the preparation of four neutral Pd(II) and Pt(II) complexes by the oxidative addition of Pd(0) and Pt(0) to bis(orthoformyl)phenyl disulfide and bis(orthoformyl)phenyl diselenide. Chapter 5 deals with the synthesis of 2-(2'-(methylseleno)phenyl)benzimidazole from 2-(methylseleno)benzaldehyde and 1,2-diamino benzene, and its coordination properties towards Pd(II) and Pt(II) ions. Reaction of this ligand with Pd(II) and Pt(II) afforded square planar complexes where two benzimidazole moieties are coordinated to the metal centre in cis fashion. Further, the complexation property of oxygen and sulfur analogues of selenium based benzimidazole ligand was studied. In contrast to the selenium based benzimidazole ligand, oxygen and sulfur analogues did not form any complex with Pd(II) and Pt(II) under similar reaction conditions. Preparation of the oxygen, sulfur and selenium containing reduced fluorenoazomethine podands and their recognition properties towards first row transitional metals are discussed in chapter 6. The N, O donor podand acts as a ‘turn-off’ probe towords Co(II), Fe(II), Fe(III) and Cu(II). whereas, N, S donor podands and N, Se donor podands act as the ‘turn-on’ probes towards Co(II), Fe(II), Fe(III) and Cu(II).

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