ic201423q_si_001.pdf (254.91 kB)
Luminescence Rigidochromism and Redox Chemistry of Pyrazolate-Bridged Binuclear Platinum(II) Diimine Complex Intercalated into Zirconium Phosphate Layers
journal contribution
posted on 2012-03-05, 00:00 authored by Eladio
J. Rivera, Cindy Barbosa, Rafael Torres, Harry Rivera, Estevao R. Fachini, Tyler W. Green, William B. Connick, Jorge L. ColónThe 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.