Mononuclear and oligonuclear transition metal complexes with acyclic and macrocyclic ligands

Abstract

Chapter 1 describes an efficient multi-step synthesis of an endotopic but sterically un¬hindered biisoquinoline decorated with long alkyl groups for better solubility. This chelate is ideally suited for macrocycle formation around transition metal ions and therefore a valuable new building block for topological chemistry. Sokolov’s concept to use an octahedral metal template for the syntheses of macrocycles and molecular knots is discussed in Chapter 2. The concept was successfully realised for the synthesis of a macrocyclic, hexadentate ligand that incorporates three bipyridine units. One-to-one complexes with this ligand and zinc(II), iron(II) and ruthenium(II) were prepared and a crystal structure of the latter was obtained. Three novel oligonuclear, macrocyclic ruthenium(II) complexes are presented in Chapter 3. The complexes are mononuclear, dinuclear and trinuclear and were prepared from bidentate, tetradentate or hexadentate macrocyclic ligands, respectively. The compounds were extensively characterised and their physical properties have been investigated. Chapter 4 describes the diversification of ligand families into neocuproin (suited for coordination to copper(I)), ferroin (suited for coordination to iron(II)) and heteroditopic structure type. Proof-of-principle conversion into palladium(II) and copper(I) complexes were prepared and their structures are discussed. The synthesis of a symmetric bipyridine ligand which possesses pyrene domains is shown in Chapter 5. Homoleptic and heteroleptic iron(II) and ruthenium(II) complexes with this ligand are presented and their solid state structures and photo¬physical properties are examined.