Design, synthesis and characterization of functional polymeric architectures with ruthenium(II) chromophoric subunits

Due to their varied structures, physical properties, and reactivities, metal complexes play a vital role in macromolecules. In this regard, new routes to a series of polymer forming ligands and their ruthenium tris (α-α ′ diimine) reagents of various peripheral functionalities have been prepared and characterized. Conventional analytical methods consisting of 1-D and 2-D NMR, mass spectrometry, electronic absorption and emission, elemental and electrochemical analyses were used to determine their structures in solution. The first X-ray single crystal structures of Ru(bpy)_n(pqX) _3−n(PF₆)₂, (pq = 2-(2-pyridyl)-4-(X)-quinoline, X = COOCH₃, n = 1, 2, 3) including the 2-(2-pyridyl)-4-carbonylmethylquinoline ligand and cis-dichloro bis-2-(2-pyridyl)-4-carbonylmethylquinoline ruthenium known today have been obtained.; These functional ligands as well as the metallo-reagents were utilized in various polymerization methodologies and post-polymer modification reactions. Complexes with carboxylic acid functionalities were ideal for post-polymer reactions of a preformed reactive polymer chain. Ligand derivatives and their terminal halide functionalized Ru complexes were used as initiators for the polymerization of functional N-(ω′-alkylcarbazolyl)methacrylates and styrene by atom transfer radical polymerization (ATRP) to produce linear and star polymers with ligands and chromophores as discrete positions in the polymer architecture. Alcohol ligands and their Ru containing complexes were utilized for ring-opening polymerization (ROP) of (ϵ-caprolactone) for the generation of telechelic ruthenium-centered polyesters of various hierarchy.; These polymers were assembled by a divergent metal-template assisted polymerization approach, which uses well-characterized metal complexes to ring open (ϵ-caprolactone) monomer. The same polymers were also obtained via a macroligand approach, which entails the synthesis of quinoline and bipyridine ligands incorporating PCL chains and subsequent chelation of these macroligands to metal precursors.; Systematic variations of polymer architecture were achieved through manipulation of the ligand set surrounding the metal template. Polymer composition was modified using an array of monomers, and, for block copolymers, via the order of monomer addition and selection. An air stable ATRP catalyst based on a [Ru(p-cymene)Cl₂]₂ complex and its first known crystal structure has been achieved.; Further derivatization of these multifunctional polymeric materials with tagged luminophores and their potential application in optical materials was also explored.