title: Layered inorganic materials as redox agents: ferrocenium-intercalated zirconium phosphate.
abstract: The direct intercalation reaction of ferrocene (bis(eta5-cyclopentadienyl)iron(II), Fc) with a highly hydrated layered zirconium phosphate (ZrP) resulted in the formation of the ferrocenium ion (Fc+) within the ZrP material. The Fc+-intercalated ZrP material has an interlayer distance of 10.7 A. The intercalated material was used as an electron acceptor for the oxidation of both ferro-cytochrome c and the excited state of tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)3]2+). Upon contact of the material with a 1.5 x 10(-5) M solution of ferro-cytochrome c, the UV-vis absorption spectrum shows the successful formation of ferri-cytochrome c. Luminescence spectroscopy shows that the Fc+-intercalated ZrP material quenches the luminescence of [Ru(bpy)3]2+. The excited-state quenching mechanism of [Ru(bpy)3]2+* by Fc+-intercalated ZrP follows a dynamic plus sphere of action model. The second-order dynamic quenching rate constant kq is 2.2 x 10(8) M(-1) s(-1).
authors.affiliation: Department of Chemistry, P.O. Box 23346, University of Puerto Rico, Río Piedras, P.R. 00931-3346.
authors.forename: Mitk'El B
authors.initials: MB
authors.lastname: Santiago
authors.forename: Chasterie
authors.initials: C
authors.lastname: Declet-Flores
authors.forename: Agustín
authors.initials: A
authors.lastname: Díaz
authors.forename: Meredith M
authors.initials: MM
authors.lastname: Vélez
authors.forename: Myrna Zoé
authors.initials: MZ
authors.lastname: Bosques
authors.forename: Yannis
authors.initials: Y
authors.lastname: Sanakis
authors.forename: Jorge L
authors.initials: JL
authors.lastname: Colón
mesh_terms: D015082:2,2'-Dipyridyl / Q000031:analogs & derivatives / Q000737:chemistry; D002412:Cations; D056831:Coordination Complexes; D003574:Cytochrome c Group / Q000737:chemistry / Q000378:metabolism; D004579:Electron Transport; D005296:Ferrous Compounds / Q000737:chemistry*; D007364:Intercalating Agents / Q000737:chemistry*; D007700:Kinetics; D049449:Luminescence; D000075163:Metallocenes; D008956:Models, Chemical; D010084:Oxidation-Reduction; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet; D015040:Zirconium / Q000737:chemistry*; D017975:Ruthenium Compounds
chemical_list: D015082:2,2'-Dipyridyl; D002412:Cations; D056831:Coordination Complexes; D003574:Cytochrome c Group; D005296:Ferrous Compounds; D007364:Intercalating Agents; D000075163:Metallocenes; D015040:Zirconium; C547232:tris(2,2-bipyridine)-ruthenium(II); D017975:Ruthenium Compounds; C027006:zirconium phosphate; C004998:ferrocene