Layered Zirconium Phosphate Chloride Dimethyl Sulfoxide as a Two-Dimensional Exchanger of Anionic Ligands. Part I. Substitution of Chloride with Inorganic Monodentate Ligands

Abstract

Crystalline ZrPO(4)Cl(CH(3))(2)SO was prepared by direct precipitation in the presence of oxalic acid as a zirconium complexing agent. The structure of ZrPO(4)Cl(CH(3))(2)SO, refined with the Rietveld method using X-ray powder diffraction data, was confirmed to be close to that of the compound prepared using gamma-zirconium phosphate as a precursor. Chloride anions directly bonded to zirconium were found to act as weak ligands; this made possible their replacement with other monodentate anionic ligands. The preparation and a preliminary characterization of a series of inorganic derivatives obtained by topotactic replacement of Cl with OH, Br, MSO(4) (M = H, NH(4), Na), NaMoO(4), and HCrO(4) anions is reported. The possibility of replacement of chloride also with organic anions, such as alkoxides and carboxylates, and the possibility of substituting also dimethyl sulfoxide with other neutral ligands, as shown by preliminary study, makes ZrPO(4)Cl(CH(3))(2)SO a useful and very flexible precursor for materials chemistry.

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

“…As we mentioned earlier, a layer of phosphates sustains the zirconium metals whose apical bonds are bonded to negative and neutral basic species, both pointing to the interlayer space (bottom of Figure 1). In the starting lambda structure, each zirconium is typically bonded to chloride anion and neutral Phosphoric Acid Industry -Problems and Solutionsdimethylsulphoxide molecule [48,49] which, in principle, can be replaced by any organic chemical structure, that is, carboxylates and amines, in a topotactic manner [32][33][34]45]. Recently, we have prepared several new soft and rigid phosphate-based λ-type organic-inorganic two-dimensional (2D) and 3D frameworks with variable porosity [10,20,32,34].…”

Lambda-zirconium phosphate covalently pillared with 1,4-biphenyldicarboxylate: a new λ-type rigid microporous framework

“…More recently, the Cl-phase [k-ZrPO 4 Cl(dmso)] was prepared by Alberti et al by two different methods: (1) postsynthetic modification method using the pristine c-ZrP as precursor [10], (2) one-pot synthesis method using oxalic acid as zirconium complexing agent [11]. The structural components of the Cl-phase are shown in Fig.…”

“…This poor reactivity of the F-phase could be ascribed to the high affinity of the inorganic layers to the fluoride anion [11], where the F -is more strongly sigma donor ligand than Cl -. Therefore, all the attempts to replace the fluoride ligand of the F-phase with other organic or inorganic ones were unsuccessful [11].…”

“…This poor reactivity of the F-phase could be ascribed to the high affinity of the inorganic layers to the fluoride anion [11], where the F -is more strongly sigma donor ligand than Cl -. Therefore, all the attempts to replace the fluoride ligand of the F-phase with other organic or inorganic ones were unsuccessful [11]. On the contrary, several organic and inorganic derivatives have been prepared using the more reactive Cl-phase as precursor [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16].…”

“…In this context, there are very few examples in the literature about the synthesis of organic-or inorganic-inorganic materials based on k-ZrP [11][12][13][14][15][16]. Therefore, any contribution to investigate the potential of this substrate can be of interest.…”