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.

Preparation of Zirconium Phosphate Nanomaterials and Their Applications as Inorganic Supports for the Oxygen Evolution Reaction

“…As the intercalation proceeds, the intercalant enters the interlayer space though the edges and diffuses into the center of the solid [73]. The direct intercalation of several guest species into θ-ZrP has been successfully used to produce composite materials for different applications [18,20,[74][75][76][77][78][79]. Reproduced from [13], with permission from the American Chemical Society, 2003.…”

Luminescence variation by rigidity control of acrylic composite materials

“…31 The luminescent rigidochromic complexes such as the well known W(CO) 4 L and X-Re(CO) 3 L (X, halogen, L ¼ pyridine derivatives) have been used as spectroscopic probes in monitoring the curing processes of organic polymers, 32 and in analysing the microscopic physical properties of silica sol-gel materials. 33 Although the rigidochromism phenomenon has been reported to explain the photoluminescence properties of several materials based on transition metal complexes, [34][35][36] here, our original approach resides in exploiting the rigidochromic properties for obtaining materials with variable optical properties by the way of selecting the matrix.…”

Effects of the carboxyl‐ended hyperbranched polyester/platinum complex molecular weight on hydrosilylation activity and self‐assembled morphology

“…This gave further evidence for the coordination between platinum ions and the carboxyl group of HTD‐ n . The peaks around 73.0 and 76.3 eV [Figure (d)] were attributed to Pt 4 f 7/2 and Pt 4 f 5/2 electrons, confirming the presence of Pt (IV) in the HTD‐ n –Pt catalysts because the BEs of the Pt 4 f 7/2 and Pt 4 f 5/2 electrons of Pt(0) usually appear at about 71.2 and 74.5 eV …”