NDLI: Syntheses, crystal structures and SHG properties of a series of polar alkali-metal molybdenum(VI) selenites based on strandberg-type $[Mo_{5}O_{15}(SeO_{3})

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Kong, Fang Zhou, Tian-hua Mao, Jiang-gao Hu, Chun-li Xu, Xiang
Description	Author Affiliation: Kong F ( State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, PR China.)
Abstract	Four new quaternary molybdenum selenites , namely, $HRb_{3}(Mo_{5}O_{15})(SeO_{3})_{2}(H_{2}O)_{2}1,$ $α-Rb_{4}Mo_{5}O_{15}(SeO_{3})_{2}(H_{2}O)_{2}2,$ $β-Rb_{4}Mo_{5}O_{15}(SeO_{3})_{2}(H_{2}O)_{2}3$ and $K_{4}Mo_{5}O_{15}(SeO_{3})_{2}(H_{2}O)_{2}4$ were synthesized by hydrothermal reactions. All of the four compounds feature a zero-dimensional (0D) $[(Mo_{5}O_{15})(SeO_{3})_{2}]^{4−}$ anionic unit composed of a five-member $MoO_{6}$ octahedral ring capped by two $SeO_{3}^{2−}$ trigonal pyramids, with the $Rb^{+}/K^{+}$ or/and $H^{+}$ cations and water molecules acting as spacers and keeping charge balance. Although these compounds exhibit similar chemical formula, their structures are slightly different. $HRb_{3}(Mo_{5}O_{15})(SeO_{3})_{2}(H_{2}O)_{2}1$ crystallizes in a polar space group $(Pca2_{1}).$ $α-Rb_{4}Mo_{5}O_{15}(SeO_{3})_{2}(H_{2}O)_{2}2$ crystallizes in a centrosymmetric (CS) space group $(P2_{1}/n)$ whereas $β-Rb_{4}Mo_{5}O_{15}(SeO_{3})_{2}(H_{2}O)_{2}3$ and $K_{4}Mo_{5}O_{15}(SeO_{3})_{2}(H_{2}O)_{2}4$ are isomorphous, crystallize in a chiral space group (C2). The chiral structures of 3 and 4 contain two similar polyanions of $[Mo_{5}O_{15}(SeO_{3})_{2}]^{4−}$ with opposite handedness. Second-harmonic-generation (SHG) measurements indicate that 1, 3 and 4 are all SHG-active. Compound 1 displays a weak SHG response of about 20% of that of KDP $(KH_{2}PO_{4})$ and is phase-matchable whereas the SHG responses of 3 and 4 are very weak (less than 5% of that of KDP). Thermal analyses and optical property measurements have also been performed.
ISSN	14779226
Issue Number	18
Journal	Dalton Trans.
Volume Number	41
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2012-05-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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