New nonlinear optical potassium iodate K[IO{sub 3}] and borates K{sub 3}[B{sub 6}O{sub 10}]Br, KTa[B{sub 4}O{sub 6}(OH){sub 4}](OH){sub 2}{center_dot}1.33H{sub 2}O-Synthesis, structures and relation to the properties
- Department of Chemistry, Lomonosov Moscow State University, Leninskije Gory 1, 119991 GSP-1 Moscow (Russian Federation)
- Department of Geology, Lomonosov Moscow State University, Leninskije Gory 1, 119991 GSP-1 Moscow (Russian Federation)
Three optically uniaxial non-centrosymmetric potassium compounds, iodate K[IO{sub 3}] and two borates K{sub 3}[B{sub 6}O{sub 10}]Br, KTa[B{sub 4}O{sub 6}(OH){sub 4}](OH){sub 2}{center_dot}1.33H{sub 2}O have been synthesized and characterized by single-crystal X-ray diffraction. The materials were synthesized through hydrothermal techniques using initial reagents and mineralizers. All the compounds are trigonal-hexagonal: the space groups are R3 (K[IO{sub 3}]), R3m (K[B{sub 6}O{sub 10}]Br) and P-62m (KTa[B{sub 4}O{sub 6}(OH){sub 4}](OH){sub 2}{center_dot}1.33H{sub 2}O). Powder second-harmonic generation (SHG) measurements on crystals, using 1064 nm Nd:YAG laser radiation, indicate the materials are all phase-matchable and have strong second-order nonlinearities. The correlation with the perovskite structure has been found and described for K,Br-borate and K-iodate. Structure-properties relation is discussed and attributed to stereo-active lone-pair on I{sup 5+} and asymmetrical bonds in the compounds. The role of K atoms is pronounced from crystal chemistry point of view, contributing optical nonlinearities. - Graphical abstract: Structure-properties relation is attributed to stereo-active lone-pair on I{sup 5+} and asymmetrical bonds in the compounds with the crucial role of K atoms, K[IO{sub 3}] structure along 3-fold axis with umbrella-like IO{sub 3}-group and with octahedral coordination-analog with perovskite. Highlights: Black-Right-Pointing-Pointer Syntheses in hydrothermal conditions trigonal KIO{sub 3}, K{sub 3}[B{sub 6}O{sub 10}]Br and KTa[B{sub 4}O{sub 6}(OH){sub 4}](OH){sub 2}. Black-Right-Pointing-Pointer Correlation with the perovskite, found for K-iodate and K,Br-borate. Black-Right-Pointing-Pointer Structure-properties relation, attributed to I{sup 5+} lone-pair and asymmetric bonds including K-atoms. Black-Right-Pointing-Pointer The compounds are phase matchable and strongly nonlinear from powder SHG measurements. Black-Right-Pointing-Pointer Averaged second-order nonlinear coefficients Left-Pointing-Angle-Bracket d Right-Pointing-Angle-Bracket are 24, 2.8 and 1.9 pm/V.
- OSTI ID:
- 22149888
- Journal Information:
- Journal of Solid State Chemistry, Vol. 195; Other Information: Copyright (c) 2012 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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