Spectro-electrochemical study of iron and ruthenium bis-terpyridine complexes with methyl viologen-like subunits as models for supramolecular polymers.

Metallo-supramolecular polyelectrolytes (MEPE) have a variety of attractive properties concerning electrochromism, spin-crossover, rheology, and cell differentiation. Previous studies suggest that these polynuclear structures can be regarded as an assembly of individual subunits and mononuclear complexes can act as models. In this study, we synthesize a monotopic and a ditopic terpyridine ligand with pyridinium units as well as the corresponding iron and ruthenium MEPEs and their mononuclear counterparts. UV-vis studies show that the mononuclear complexes have similar absorption properties to MEPEs. Furthermore, all complexes and MEPEs exhibit electrochromic behavior. Yet only the MEPEs can be deposited on different substrates using a layer-by-layer approach which makes them attractive for applications as electrochromic devices. However, the low solubility particularly of the ruthenium MEPE, renders characterization in solution impractical. Hence, the use of mononuclear complexes with similar monotopic ligands as presented herein can act as a first instance to evaluate the properties of corresponding MEPEs, facilitating the development of metallo-supramolecular materials.