Transition metal containing conducting polymers and supramolecular assemblies: Syntheses, characterization and approaches to metal ion sensors

This dissertation describes syntheses and characterization of two hybrid systems as well as electrochemical and conducting studies of theses systems. One of the hybrid systems is based on Ru(bpy)$\sb3$ derivatives, Ru(1)$\sb3,$ Ru(2)$\sb3$ and Ru(3)$\sb3,$ which are substituted with polymerizable dithienyl groups. Their corresponding polymers, PolyRu(1)$\sb3,$ PolyRu(2)$\sb3$ and PolyRu(3)$\sb3,$ produced by anodic electrochemical polymerization, exhibit two regions of electrochemical activity at oxidative and reductive potentials in their cyclic voltammograms. High redox conductivity in both the ligand-based oxidation and the metal-based reduction processes are found for PolyRu(2)$\sb3$ and PolyRu(3)$\sb3.$ In the case of PolyRu(1)$\sb3,$ only the metal-based reduction processes resulted in high redox conduction.* The other system is based on polymetallorotaxanes, PolyRot(1,M) and PolyRot(2,M), (M = Zn$\sp{2+}$ or Cu$\sp{1+}),$ which are produced by oxidative polymerization of metallorotaxanes, Rot(1,M) and Rot(2,M). The investigations of the electrochemical, conducting, and optical properties of PolyRot(1,M) and PolyRot(2,M) indicated that the polymetallorotaxane\u27s redox and conducting properties were dramatically affected by the Lewis acidic and redox properties of the coordinated metal ions. The matching of the polymer and Cu$\sp{1+/2+}$ couple redox potentials in PolyRot(2,Cu) resulted a Cu$\sp{1+/2+}$ contribution to conductivity. The metal-free PolyRot(1) and PolyRot(2) were produced by extracting the metal ions and these polymers reversibly bound Zn$\sp{2+}$ or Cu$\sp{2+}$ ions in solution. The Cu$\sp{2+}$ dopes the films of PolyRot(2) and Poly(2), which have lower oxidation potential than those of PolyRot(1), to produce 10$\sp6$-10$\sp7$-fold conductivity increases. In the case of PolyRot(1) and Poly(1), the rotaxane structure was demonstrated to be key for reversible complexation of metal ions.* New surfactants incorporating paramagnetic oxo-vanadium centers I, II, III, and IV will also be described, which display high stability in aqueous environments and lyotropic behavior.* ftn*Please refer to the dissertation for diagrams