Chapter 1 Introduction
There is currently a growing interest in the development of lanthanide (Ln) containingsupramolecular structures and more specifically the design and synthesis of near infrared(NIR)
emitting lanthanide complexes.
This is mainly due to the application of thesecomplexes in chemical sensing and imaging.
Within the field of Medicinal Chemistry thesecomplexes are of particular interest due to their use in bio-related applications such asimmunoassays and imaging. This report will show the synthesis and the sensing ability of such emitting sensors for zinc.
1.1 Lanthanide ions
The lanthanides consist of the fifteen elements from lanthanum to lutetium in theperiodic table. They are all relatively similar in that they consist of a 4
open shellconfiguration with a regular and small decrease in atomic radii. This decrease in radii, knownas lanthanide contraction, is due to the weak shielding of the
electrons and the increasingatomic number. The lanthanides favour a + 3 oxidation state with a [ Xe]4
configurationand are described as hard Lewis acids.
Being hard Lewis acids means the ions have highcharge density and a strong electrostatic nature, which results in a high affinity for ligandsthat can be easily polarised and are hard Lewis bases, possess one or several donor atomssuch as oxygen or nitrogen.Lanthanides possess high coordination requirements, usually 9
10 coordinatedligands, and so multidentate macrocyclic and acyclic ligands are often used. In forminglanthanide complexes, 1,4,7,10-tetraazacyclododecane, also known as cyclen, is a ligandwhich is often used as it consists of four nitrogens in the cyclen ring and four to fivecoordination sites, with carboxylates being commonly used at these sites, as in DOTA and itsderivatives, fulfilling the high coordination requirements of the lanthanides.