Synthesis and physico-chemical studies on dithiolene complexes of the closed-shell (d10) metals and trivalent lanthanide ions

Abstract

Nowadays, chemistry represents a general tool for accessing (synthesis), controlling (parameters influence) and understanding (study of properties) the material. This is allowed by two possible approaches: the "Top-down'; and "Bottom-up';. The first approach is a key to nanotechnology. The second approach consists in assembling small systems, with intrinsic properties, to build up macro system with interesting properties. This concept is generally termed as: "from molecules to material'; and in this context, supramolecular chemistry plays a crucial role. The present work examines the synthesis and properties of dithiolene systems bearing metal ions and lanthanides. The first chapter is a general introduction on dithiolene chemistry and lanthanides. The second chapter deals with the synthesis and characterisation of supramolecular systems based on neutral dithiolene-like ligands. In this chapter, importance of non-covalent interactions is discussed. The third chapter concerns the reactivity of these neutral dithiolene-like ligands towards d10 transition metals (CuI, HgII, AuI). This chapter will describe the synthesis of supramolecular complexes and their spectroscopic properties. The fourth chapter deals with the reactivity of the ligands with lanthanides (Nd, Eu, Gd, Tb, Er) and the characterisation of Ln3+-dithiolene complexes. The discussion will be oriented on the energy transfer process taking place in these coordination compounds ("Antenna Effect';).