Engineering of Microcrystaline Solid-State Networks Using Cross-Linked γ-Zirconium Phosphate/Hypophosphite with Nonrigid Polyethylenoxadiphosphonates. Easy Access to Porously Dynamic Solids with Polar/Nonpolar Pores

Abstract

The construction of organic−inorganic scaffolds based on γ-zirconium phosphate and polyethylenoxa diphosphonates is described. Microcrystalline materials with a controlled, low degree of pillaring are synthesized and characterized by elemental analysis, X-ray powder diffraction, solid-state NMR, and thermogravimetric analysis. The mechanism for the topotactic polyethylenoxa-pillaring reaction is proposed and confronted with previous ones suggested for the reaction of nonpolar organic diphosphonates. The affinity among the polyethylenoxa chains and the superficial acidic phosphates of the layered salt is thus clearly evidenced. The work shows how the inner structure of the pillared microcrystals may be easily modified by a second exchange of the remaining superficial phosphates by other phosphorus species as the low-polar hypophosphite. The rigidity of the layers and the wedge-like effect of intercalated amines at the edges of the microcrystals cause them to increase the interlayer distance, and hence porosity, in a flash fashion.

Complex Hydrothermal Reaction Systems: A Systematic Investigation of Copper Phosphonatoethanesulfonates by High‐Throughput Methods

“…These compounds are mostly based on metal carboxylates, sulfonates, and phosphonates and are intensively investigated due to their potential applications as sorbents, ion exchangers, catalysts, or charge-storage materials. [2,3] Porous hybrid compounds based on metal carboxylates [4][5][6] and phosphonates [7][8][9][10] have attracted widespread interest in the past few years. We are interested in the use of organic ligands containing two or more different functional groups for the synthesis of functionalized porous hybrid compounds or bimetallic hybrid systems.…”

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.…”

“…[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.…”

Phosphate-Based Organic-Inorganic Hybrid Materials: Design, Construction and Technological Applications

“…Pillars could be either rigid or non-rigid, the latter being the most versatile as the porosity of the materials can be controlled by simple chemical means [35][36][37][38]. The outstanding features of these materials come from their ability to combine the properties of both the organic pendant groups with those of the inorganic host [39].…”