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Issue 7, 2018
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New complex phosphates Cs3MIIBi(P2O7)2 (MII – Ca, Sr and Pb): synthesis, characterization, crystal and electronic structure

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Abstract

Herein, the peculiarities of complex phosphate formation in self-fluxes of Cs–MII–Bi–P–O (MII = Ca, Sr, Ba and Pb) systems with Cs/P = 0.7–1.3 at fixed ratios of Bi/P = 0.2 and Bi/MII = 1.0 were studied and discussed. Three novel isostructural diphosphates with the general composition Cs3MIIBi(P2O7)2 (MII = Ca, Sr and Pb) and the original framework topology were synthesized and characterized via single-crystal and powder X-ray diffraction, SEM, DTA, and FTIR- and UV-VIS-spectroscopy. In addition, electronic structure (DFT) and Voronoi–Dirichlet polyhedra (VDP) characteristics calculations and crystallochemical analysis were performed. In the structure of the new compounds, the MIIO7 and BiO6 polyhedra are connected via common oxygen vertices forming infinite helical-like chains, which are linked by P2O7 groups into a 3D-framework with pentagonal tunnels, where the Cs+ cations are located. The structural peculiarities are discussed considering perspectives for the creation of new luminescent materials. The dielectric bandgaps, Eg, of the Cs3MIIBi(P2O7)2 crystals reveal an ∼0.2 eV low-energy shift in the Ca–Sr–Pb sequence of MII cations, which reveals the possibility to tune the optical absorbance spectra of the crystals via the synthesis of solid solutions with various contents of MII cations. The glass-ceramic synthetic approach is also proposed as a convenient method for the creation of new diphosphates, and the applicability of this method is verified for Cs3CaBi(P2O7)2.

Graphical abstract: New complex phosphates Cs3MIIBi(P2O7)2 (MII – Ca, Sr and Pb): synthesis, characterization, crystal and electronic structure

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Publication details

The article was received on 30 Nov 2017, accepted on 06 Jan 2018 and first published on 08 Jan 2018


Article type: Paper
DOI: 10.1039/C7DT04505K
Citation: Dalton Trans., 2018,47, 2274-2284
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    New complex phosphates Cs3MIIBi(P2O7)2 (MII – Ca, Sr and Pb): synthesis, characterization, crystal and electronic structure

    I. V. Zatovsky, N. Yu. Strutynska, Y. A. Hizhnyi, V. N. Baumer, I. V. Ogorodnyk, N. S. Slobodyanik, I. V. Odynets and N. I. Klyui, Dalton Trans., 2018, 47, 2274
    DOI: 10.1039/C7DT04505K

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