Sensitized Luminescence of Lanthanides within the Walls of Polyethylenoxa-Pillared γ-Zirconium Phosphate

Abstract

Pillared γ-zirconim phosphate at low level with a diphosphonic acid resulting from the addition of pentaethyleneglycol to diethyl vinyl phosphonate was prepared and used as a porous matrix to intercalate LnCl3 (Ln = Eu, Tb) and 2,2-bipyridyl (bpy). The uptake levels of both species in mild conditions were 0.35 and 0.10 equivalents per Zr, respectively. Strong interactions between the lanthanide ion and the polyethylenoxa chains were evidenced. Although powder XRD of the composite showed two interlayer distances (1.7 and 2.2 nm) indicating that the material was not homogeneous, excitation luminescence spectra confirmed strong lanthanide bpy-sensitized emission which was more than 50 times higher than that in nonpillared γ-zirconium phosphate.

The use of lanthanide luminescence as a reporter in the solid state: Desymmetrization of the prochiral layers of γ-zirconium phosphate/phosphonate and circularly polarized luminescence

“…These reactions were performed as previously described [5]. A certain amount of γ-ZrP or the topotacticaly exchanged solid phase was suspended in an aqueous solution 0.1 M of optically pure 1-phenylethylamine (100 mL of solution per g of solid) and the mixture was vigorously stirred at room temperature for 48 h. The solid was then centrifuged, washed three times with deionized water and ethanol, dried at 100 °C for 3 h and conditioned over saturated solution of BaCl 2 .…”

“…On the other hand, we have also shown that appropriate γ-ZrP matrices are able to produce the sensitized emission of lanthanides by the well-known antenna effect . For instance, the material bearing diphosphonate 1 (Scheme 1) and intercalated with 2,2′-bipyridyl gave rise to strong Eu(III) and Tb(III) luminescence when these ions were intercalated as well into the layered matrix [5]. The sensitized luminescence was also achieved with γ-ZrP pillared with diphosphonate 4 (Scheme 1) [6].…”

A Luminescence and Electrochemical Study of Photoinduced Electron Transfer within the Layers of Zirconium Phosphate

“…General Procedures: Intercalation of Ru(bpy) 3 in c-ZrP: The complex dissolved in water (concentration, c = 1 mg mL -1 ) was added over a dispersion of c-ZrP (c = 10 mg mL -1 ; see our previous papers for the preparation of the inorganic salt [6][7][8][9][10][11][12]) in a 1:1 mixture of water/acetone previously heated at 80°C. The temperature was maintained for 24 h, the dispersion allowed to cool at room temperature (RT) and then centrifuged.…”

“…This diminution could be the consequence of the covalent bonding, the shortest separation being that of the pillared material (8).…”

“…[4] ZrP [5] is an excellent example. It constitutes a lamellar template that we regularly use [6] to obtain a number of microcrystalline materials with outstanding properties, ranging from molecular recognition, [7] luminescence, [8] post-synthesis variable porosity, [9] chiral memory, [10] hydrogen storage, [11] and electron transfer in the solid state. [12] This paper is concerned with the latter topic.…”