title: Luminescence rigidochromism and redox chemistry of pyrazolate-bridged binuclear platinum(II) diimine complex intercalated into zirconium phosphate layers.
abstract: The direct intercalation of a pyrazolate-bridged platinum(II) bipyridyl dimer ([{Pt(dmbpy)(μ-pz)}(2)](2+); dmbpy = 4,4'-dimethyl-2,2'-bipyridine, pz(-) = pyrazolate) within a zirconium phosphate (ZrP) framework has been accomplished. The physical and spectroscopic properties of [{Pt(dmbpy)(μ-pz)}(2)](2+) intercalated in ZrP were investigated by X-ray powder diffraction and X-ray photoelectron, infrared, absorption, and luminescence spectroscopies. Zirconium phosphate layers have a special microenvironment that is capable of supporting a variety of platinum oxidation states. Diffuse reflectance spectra from powders of the blue-gray intercalated materials show the formation of a low-energy band at 600 nm that is not present in the platinum dimer salt. The nonintercalated complex is nonemissive in room-temperature fluid solution, but gives rise to intense blue-green emission in a 4:1 ethanol/methanol 77 K frozen glassy solution. Powders and colloidal suspensions of [{Pt(dmbpy)(μ-pz)}(2)](2+)-exchanged ZrP materials exhibit intense emissions at room-temperature.
authors.affiliation: Department of Chemistry, University of Puerto Rico, P.O. Box 23346, Río Piedras, P.R. 00931.
authors.forename: Eladio J
authors.initials: EJ
authors.lastname: Rivera
authors.forename: Cindy
authors.initials: C
authors.lastname: Barbosa
authors.forename: Rafael
authors.initials: R
authors.lastname: Torres
authors.forename: Harry
authors.initials: H
authors.lastname: Rivera
authors.forename: Estevao R
authors.initials: ER
authors.lastname: Fachini
authors.forename: Tyler W
authors.initials: TW
authors.lastname: Green
authors.forename: William B
authors.initials: WB
authors.lastname: Connick
authors.forename: Jorge L
authors.initials: JL
authors.lastname: Colón