Photogenerated avenues in macromolecules containing Re(i), Ru(ii), Os(ii), and Ir(iii) metal complexes of pyridine-based ligands

Pyridine-based ligands, such as 2,2'-bipyridine and 1,10-phenanthroline, have gained much interest in the fields of supramolecular chemistry as well as materials science. The appealing optoelectronic properties of their complexes with heavy d(6) transition metal ions, such as Ru(ii), Os(II), Re(I) and Ir(III), primarily based on the metal-to-ligand charge-transfer (MLCT) nature featuring access to charge-separated states, have provided the starting point for many studies in the field of dye-sensitized solar cells (DSSCs), organic light emitting diodes (OLEDs), artificial photosynthesis and photogenerated electron as well as energy transfer processes. This critical review provides a comprehensive survey over central advances in the field of soluble metal-containing macromolecules in the last few decades. The synthesis and properties of functionalized 2,2'-bipyridyine- and 1,10-phenanthroline-based d(6) metal complexes, in particular, their introduction into different prevailing polymeric structures are highlighted. In the most part of the review metal complexes which have been attached as pendant groups on the polymer side chain are covered. Selected applications of the herein discussed metal-containing macromolecules are addressed, particularly, with respect to photogenerated electron/energy transfer processes. In order to enable a deeper understanding of the properties of the ligands and metal complexes, the fundamentals of selected photophysical processes will be discussed (223 references).