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Luminescence Rigidochromism and Redox Chemistry of Pyrazolate-Bridged Binuclear Platinum(II) Diimine Complex Intercalated into Zirconium Phosphate Layers

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journal contribution
posted on 05.03.2012 by Eladio J. Rivera, Cindy Barbosa, Rafael Torres, Harry Rivera, Estevao R. Fachini, Tyler W. Green, William B. Connick, Jorge L. Colón
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.