Crystal structure, vibrational, spectroscopic and thermochemical properties of double sulfate crystalline hydrate [cseu(H2o)3(so4)2]·h2o and its thermal dehydration product cseu(so4)2

Описание

Тип публикации: статья из журнала

Год издания: 2021

Идентификатор DOI: 10.3390/cryst11091027

Ключевые слова: crystal structure, dehydration, photoluminescence, raman, sulfate, thermal stability

Аннотация: Crystalline hydrate of double cesium europium sulfate [CsEu(H2O)3(SO4)2]·H2O was syn-thesized by the crystallization from an aqueous solution containing equimolar amounts of 1Cs+:1Eu3+:2SO42− ions. Anhydrous salt CsEu(SO4)2 was formed as a result of the thermal dehydration of the crystallohydrate. The unusual effects observed durinПоказать полностьюg the thermal dehydration were attributed to the specific coordination of water molecules in the [CsEu(H2O)3(SO4)2]·H2O structure. The crystal structure of [CsEu(H2O)3(SO4)2]·H2O was determined by a single crystal X-ray diffraction analysis, and the crystal structure of CsEu(SO4)2 was obtained by the Rietveld method. [CsEu(H2O)3(SO4)2]·H2O crystallizes in the monoclinic system, space group P21/c (a = 6.5574(1) Å, b = 19.0733(3) Å, c = 8.8364(2) Å, β = 93.931(1)°, V = 1102.58(3) Å3). The anhydrous sulfate CsEu(SO4)2 formed as a result of the thermal destruction crystallizes in the monoclinic system, space group C2/c (a = 14.327(1) Å, b = 5.3838(4) Å, c = 9.5104(6) Å, β = 101.979(3) °, V = 717.58(9) Å3). The vibration properties of the compounds are fully consistent with the structural models and are mainly determined by the deformation of non-rigid structural elements, such as H2O and SO42− . As shown by the diffused reflection spectra measurements and DFT calculations, the structural transformation from [CsEu(H2O)3(SO4)2]·H2O to CsEu(SO4)2 induced a significant band gap reduction. A noticeable dif-ference of the luminescence spectra between cesium europium sulfate and cesium europium sulfate hydrate is detected and explained by the variation of the extent of local symmetry violation at the crystallographic sites occupied by Eu3+ ions, namely, by the increase in inversion asymmetry in [CsEu(H2O)3(SO4)2]·H2O and the increase in mirror asymmetry in CsEu(SO4)2. The chemical shift of the5D0 energy level in cesium europium sulfate hydrate, with respect to cesium europium sulfate, is associated with the presence of H2O molecules in the vicinity of Eu3+ ion. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.

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Издание

Журнал: Crystals

Выпуск журнала: Vol. 11, Is. 9

Номера страниц: 1027

ISSN журнала: 20734352

Издатель: MDPI

Персоны

  • Denisenko Yuriy G. (Tyumen State Univ, Dept Inorgan & Phys Chem, Tyumen 625003, Russia)
  • Molokeev Maxim S. (Fed Res Ctr KSC SB RAS, Kirensky Inst Phys, Lab Crystal Phys, Krasnoyarsk 660036, Russia; Siberian Fed Univ, Inst Engn Phys & Radioelect, Krasnoyarsk 660041, Russia; Far Eastern State Transport Univ, Dept Phys, Khabarovsk 680021, Russia)
  • Oreshonkov Aleksandr S. (Fed Res Ctr KSC SB RAS, Kirensky Inst Phys, Lab Mol Spect, Krasnoyarsk 660036, Russia; Siberian Fed Univ, Sch Engn & Construct, Krasnoyarsk 660041, Russia)
  • Krylov Alexander S. (Fed Res Ctr KSC SB RAS, Kirensky Inst Phys, Lab Mol Spect, Krasnoyarsk 660036, Russia)
  • Aleksandrovsky Aleksandr S. (Fed Res Ctr KSC SB RAS, Kirensky Inst Phys, Lab Coherent Opt, Krasnoyarsk 660036, Russia; Siberian Fed Univ, Dept Photon & Laser Technol, Krasnoyarsk 660041, Russia)
  • Azarapin Nikita O. (Tyumen State Univ, Dept Inorgan & Phys Chem, Tyumen 625003, Russia)
  • Andreev Oleg (Tyumen State Univ, Dept Inorgan & Phys Chem, Tyumen 625003, Russia; UB RAS, Lab Chem Cpds Rare Earth Elements, Inst Solid State Chem, Ekaterinburg 620137, Russia)
  • Razumkova Illaria A. (Tyumen State Univ, Dept Inorgan & Phys Chem, Tyumen 625003, Russia)
  • Atuchin Victor V. (SB RAS, Lab Opt Mat & Struct, Inst Semicond Phys, Novosibirsk 630090, Russia; Kemerovo State Univ, Res & Dev Dept, Kemerovo 650000, Russia)