Metal complexes of alkyne-functionalised 2,2':6',2"-terpyridine ligands

4'-substituted-2,2':6',2"-terpyridine ligands which all contain a terminal
alkyne functionality are synthesised and discussed in Chapter 2. These
ligands have been designed with potential coupling to platinum(II) or gold(I)
through the alkyne in mind and have varying degrees of flexibility built in.
Ligands are intended to favour either polymer or macrocycle formation
according to their flexibility and the various ways of achieving this are also
discussed in Chapter 2.
The coupling of these ligands with platinum(II) and gold(I) are
discussed separately in Chapters 3 and 4, respectively. The combination of
the ligand flexibility with the coordination geometry at the metal centre is
carefully considered in order to form building blocks of a specific shape which
can then be reacted further at the pendant terpyridine moiety. The ligands
have been fully characterised, some crystallographically. Luminescence
spectra of these building blocks are measured. 31P NMR spectroscopy is a
particularly useful tool for characterisation of these molecules, especially in
the case of the platinum(II) complexes, since this provides a means of
determining the configuration of the phosphine ligands at the platinum(II)
centre. Again, X-ray crystal data provide some invaluable information as to
the arrangement of the molecules in the solid state, including interactions
between metal atoms in the case of Au(I).
The final step in the formation of polymers or macrocycles is discussed
in Chapter 5 where the platinum(II) and gold(I) containing building blocks are
assembled into supramolecular structures by coordination of the pendant
terpyridine moiety with iron(II). The resulting structures are fully characterised,
and electrospray ionisation mass spectrometry is important in determining the
size of the macrocycles formed. Pulsed-field gradient spin-echo NMR
experiments help to determine the size of the products formed and X-ray
crystal data for one structure have been obtained and are discussed.