The role of metal-ions in organic layers of different complexity was analysed using electrochemistry and in situ spectroelectrochemistry. Analysis developed in three stages starting from quasi two-dimensional self-assembled monolayers (SAMs), progressing to polythiophene-based metallo-polymers and finally, three-dimensional
macro-structures comprising complexing cavities.
Electrochemical data of SAMs of ferrocenyl-6-alkanethiol (FcC6) on singlecrystal platinum substrates (Pt (100] and Pt (110]) pointed to the formation of organised layers via a mechanism different to that established for the formation of
SAMs on gold. Whilst alkane thiols bind chemically to gold ( chemisorption), the same adsorbates were found to physically adsorb onto platinum substrates (physisorption). These conclusions were supported by in situ data showing the S-H IR
band in fully formed layers on platinum.
SNIFTIRS and electrochemical analysis of metal-modified polythiophenes, showed that the introduction of bipyridyl Ru and Os centres onto a polythiophene backbone led to polymers where the redox switching of the conducting polymer films
occurs via different moieties. The two functionalities, the thiophene backbone and bipyridyl centre, interact closely, exchanging charges during oxidation and reduction of the films. It was also found that the extent of the interaction was dependent on the nature of the substituents on the thiophene and the conformation of the heteroaromatic
rings. SNIFTIRS analysis also showed that the metal centres function as "electronic gates", allowing charges to be inserted into the polymer at reduced potentials.
The use of metal-templating during the synthesis of polymeric macrostructures has proven to be a pertinent way of introducing structural functionality onto polymerbased ensembles where the conducting properties of the conjugated backbone are retained. Moreover, the removal of metal-ions from the 3D structure has an impact on
the overall properties of the ensembles, thus enabling the development of tunable polymer-based materials by simple metal-ion exchange.
The synergetic use of transition metal-ion and conjugated polymers shows significant potential for the development of novel hybrid materials with applicability in diverse areas ranging from electrochemical sensors to molecular motors