pi-conjugated materials containing transition metals

In this thesis, the factors influencing the metal and organic fragment interactions in metal-containing conjugated polymers are investigated. All the compounds presented in this work were fully characterized by 1 H, 31P NMR, infrared and UV-visible spectroscopies.; In Chapter 2, the syntheses and properties of trans, trans, trans -[Ru(PBu₃)₂(CO)(L)(C≡CFc)₂] (41, L = CO; 42, L = pyridine; 43, L = P(OMe)₃; Fc = ferrocenyl), trans, trans, trans-[RuCl ₂(POMe-P)₂(FcC₆H₄NC) ₂] (44) (POMe = PPh₂C₆H₄OCH ₃), trans, trans, trans-[RuCl₂(PC2OMe- P)₂(FcC₆H₄NC)₂] ( 45) (PC2OMe = PPh₂CH₂CH₂OCH₃ ) and the mixed carbonyl-isocyanide complexes trans, trans, trans-[RuCl₂(POMe-P)₂(CO)(FcC ₆H₄NC)] (46) and trans, trans, trans -[RuCl₂(PC2OMe-P)₂(CO)(FcC ₆H₄NC)] (47) are described. Cyclic Voltammetry studies of 41–45 reveal that the ruthenium bisacetylide bridges in complexes 41–43 allow electronic interaction between the terminal ferrocenyl groups and the interaction depends on the nature of the ancillary ligands on the ruthenium. In contrast, no electronic interaction occurs between the ferrocenyl groups and the Ru centers in 44 and 45.; A series of phosphine-thiophene ligands (51–55) offering several coordination site combinations have been prepared and are described in Chapter 3. Compounds 51 (dpppth), 52a (dppterth), 52b (Me-dppterth) and 52c (Me₂-dppterth) are found to bind to metals in a mono- or bidentate fashion (P or P,S). Compound 53 (5dppterth) can only be monodentate via the phosphine while compounds 54 and 55 can bind either in a bidentate (P₂ or P,S) or monodentate fashion via one phosphine only.; Ruthenium(II) complexes [RuCl₂(dpppth-P,S) ₂] (61), [RuCl₂(dppterth- P,S1)₂] (62) and [RuCl ₂(CO)(5dppterth-P)₂] (71) are described in Chapter 4. Displacement of one of the dppterth ligands in 62 with bis(diphenylphosphino)methane (dppm) yields 66 which isomerizes in solution to 67. Complexes 61, 62, 66 and 67 react with carbon monoxide by displacing the coordinated thiophene. Complex 71 electropolymerizes to form red, conductive films which were characterized by energy dispersive X-ray (EDX), surface-reflectance IR and UV-vis spectroscopies.; Dinuclear complexes [Pd₂(μ-Cl₂)(L)₂) (72a–c) (L = 52a–c) have been prepared in which the palladium centers are in a square planar geometry and the phosphine-thiophene ligand binds via the phosphorus and a carbon of a terminal thiophene ring. This work is described in Chapter 5. Bis(phosphine) Pd(II) complexes ( 73a–c and 78) have been prepared with the ligands 52a–c and 53 and the monocationic complexes 74a–c have been synthesized from compounds 73a–c two phosphine-thiophene ligands are inequivalent. On...