Microporous framework polar silicate-germanates with a wide isomorphic substitution: (K2.9Cs0.1)(Sc0.7In0.3)[(Si2.95Ge0.05)O9]·H2O and (K2.16Cs0.84)Bi[(Si1.5Ge1.5)O9]·H2O

Anastasiia P. Topnikova; Elena L. Belokoneva; Anatoly S. Volkov; Olga V. Dimitrova; Sergey Yu. Stefanovich

doi:10.1515/zkri-2022-0056

Published by De Gruyter (O) March 13, 2023

Microporous framework polar silicate-germanates with a wide isomorphic substitution: (K_2.9Cs_0.1)(Sc_0.7In_0.3)[(Si_2.95Ge_0.05)O₉]·H₂O and (K_2.16Cs_0.84)Bi[(Si_1.5Ge_1.5)O₉]·H₂O

Anastasiia P. Topnikova , Elena L. Belokoneva , Anatoly S. Volkov , Olga V. Dimitrova and Sergey Yu. Stefanovich

From the journal Zeitschrift für Kristallographie - Crystalline Materials

https://doi.org/10.1515/zkri-2022-0056

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Abstract

New silicate-germanates (K_2.9Cs_0.1)(Sc_0.7In_0.3)[(Si_2.95Ge_0.05)O₉]·H₂O and (K_2.16Cs_0.84)Bi[(Si_0.5Ge_0.5)₃O₉]·H₂O have been synthesized in multi-component systems under mild hydrothermal conditions. The new compounds are classified as new representatives of close related K₃ScSi₃O₉·H₂O parent structure, sp. gr. Pmn2₁. Their structural and isomorphic peculiarities are compared with it as well as with earlier investigated K_1.46Pb_1.54Сa[(Ge_0.23Si_0.77)₃O₉](ОН)_0.54·0.46Н₂О. Together with other known compounds, silicate-germanates form the extensive family A₃M[T₃O₉]·H₂O, A = K, Cs, Ca, Pb; M = Ho, Sc, Lu, Tb, Er, Y, Bi, Pb, In; T = Si, Ge, with a mixed microporous framework combined of M-octahedra and T-tetrahedra. Large alkali metal or/and Ca, Pb cations fill broad framework channels with cross-section up to 7.3 Å. Because of wide isomorphic substitution in the channels, and in tetrahedra and octahedra, ion exchange properties in the family are expected. Due to polar symmetry, all the crystals possess second-order nonlinearity which was confirmed with positive SHG tests for four compositions. Powder SHG experiments demonstrated moderate second harmonic intensities of order of α-quartz standard signals.

Keywords: hydrothermal synthesis; isomorphic substitution; mixed microporous framework; second harmonic generation; silicate-germanate; single crystal structure

Corresponding author: Anastasiia P. Topnikova, Crystallography, Lomonosov Moscow State University, Faculty of Geology, Leninskie Gory 1, Moscow 119991, Russian Federation, E-mail: nastya_zorina@rambler.ru

Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: The authors are grateful to Natalia Zubkova for her aid in the collection of the experimental X-ray diffraction data and absorption correction and to Vasiliy Yapaskurt for the determination of crystal chemical composition. We are thankful to Shilie Pan and Zhihua Yang for discussion of nonlinear optical properties in a family of compounds. Anatoly Volkov was partial supported by RFBR grant No. 20-03-00702 a.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2022-08-26

Accepted: 2023-02-20

Published Online: 2023-03-13

Published in Print: 2023-03-28

Microporous framework polar silicate-germanates with a wide isomorphic substitution: (K_2.9Cs_0.1)(Sc_0.7In_0.3)[(Si_2.95Ge_0.05)O₉]·H₂O and (K_2.16Cs_0.84)Bi[(Si_1.5Ge_1.5)O₉]·H₂O

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