title: Synthesis, structural charaterization, and electrochemical and optical properties of ferrocene-triazole-pyridine triads.
abstract: The synthesis and electrochemical, optical, and cation-sensing properties of the ferrocene-triazole-pyridine triads 3 and 5 are presented. Azidoferrocene 1 and 1,1'-diazidoferrocene 4 underwent the "click" reaction with 2-ethynylpyridine to give the triads 3 and 5 in 81% and 68% yield, respectively. Electrochemical studies carried out in CH(3)CN in the presence of increasing amounts of Zn(2+), Ni(2+), Cd(2+), Hg(2+), and Pb(2+) metal cations, showed that the wave corresponding to the ferrocene/ferrocenium redox couple is anodically shifted by 70-130 mV for triad 3 and 167-214 mV for triad 5. The maximum shift of the ferrocene oxidation wave was found for 5 in the presence of Zn(2+). In addition, the low-energy band of the absorption spectra of 3 and 5 are red-shifted (Δλ = 5-10 nm) upon complexation with these metal cations. The crystal structures of compounds 3 and 5 and the complex [3(2)·Zn](2+) have been determined by single-crystal X-ray methods. (1)H NMR studies as well as density functional theory calculations have been carried out to get information about the binding sites that are involved in the complexation process.
authors.affiliation: Departamento de Química Orgánica, Facultad de Química, Campus de Espinardo, Universidad de Murcia, E-30100 Murcia, Spain.
authors.forename: Tomás
authors.initials: T
authors.lastname: Romero
authors.forename: Raúl A
authors.initials: RA
authors.lastname: Orenes
authors.forename: Arturo
authors.initials: A
authors.lastname: Espinosa
authors.forename: Alberto
authors.initials: A
authors.lastname: Tárraga
authors.forename: Pedro
authors.initials: P
authors.lastname: Molina
mesh_terms: D060326:Chemistry Techniques, Synthetic; D018360:Crystallography, X-Ray; D004563:Electrochemistry; D005296:Ferrous Compounds / Q000737:chemistry*; D000075163:Metallocenes; D008958:Models, Molecular; D015394:Molecular Structure; D055095:Optics and Photonics; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D011725:Pyridines / Q000737:chemistry*; D013237:Stereoisomerism; D014230:Triazoles / Q000737:chemistry*
chemical_list: D005296:Ferrous Compounds; D000075163:Metallocenes; D009942:Organometallic Compounds; D011725:Pyridines; D014230:Triazoles; C023666:pyridine; C004998:ferrocene