X-ray structural studies of lanthanide macrocycles and biological molecules

Abstract

The work described in this thesis is broadly divided into two sections. The structural study on the lanthanide macrocyclic complexes was afforded by means of X-ray crystallography In this chapter, the molecules dota, the cationic enantiopure tetraamide europium and dysprosium complexes, the sodium complexes of the tetranaphthylamide and quinoyl derivative, the enantiopure gadolinium and europium complexes of the tetraamide series with esteratic sidechains, the lanathanum and ytterbium complexes of the dota derivative with benzyl phosphinate sidechains, and the tetracarboxyethyl series both as three uncomplexed stereoisomer and complexes of the RRRR stereoisomer with europium, gadolinium and terbium. These complexes exhibit quite a lot of structural diversity. Chapter five deals with experiments carried out at ultra low temperatures. A phase transition that the molecule benzil undergoes is investigated on the Fddd diffractometer, a study of the interesting 1,12-dicarbonyl borane was undertaken to obtain precise values for the carbonyl bond lengths and the unprecedented structure of its hydrate was revealed to be a carbene diol and not the expected carboxylic acid complex The standard for macromolecular tests for diffraction, chicken egg white lysozyme, was crystallised and used to optimise conditions for low-temperature data acquisition from macromolecular samples The work described in this Thesis was carried out in the Department of Chemistry, Durham University from October 1995 to January 1999, under the supervision of Professor J.A.K. Howard. All of the work is my own, unless stated to the contrary, and it has not been submitted previously for a degree at this or any other university.