Variable Asymmetric Chains in Transition Metal Oxyfluorides: Structure-Second-Harmonic-Generation Property Relationships

Inorganic Chemistry
Belal AhmedKang Min Ok

Abstract

Four novel transition metal oxyfluorides, [Zn(pz)3][MoO2F4]·0.1H2O (1), [Zn(pz)2F2][Zn(pz)3]2[WO2F4]2 (2), [Cd(pz)4][Cd(pz)4(H2O)][MoO2F4]2·0.625H2O (3), and [Zn(mpz)3]2[MoO2F4]2 (4) (pz = pyrazole; mpz = 3-methyl pyrazole) have been synthesized. Compounds 1 and 4 contain helical chains. Compound 2 accommodates zigzag chains, and compound 3 has quasi-one-dimensional linear chains. The variable chain structures are found to be attributable to the different structure-directing anionic groups and hydrogen bonding interactions. Compound 4 crystallized in the noncentrosymmetric (NCS) polar space group, Pna21, is nonphase-matchable (Type I), and reveals a moderate second-harmonic-generation (SHG) efficiency (10 × α-SiO2). The observed SHG efficiency of compound 4 is due to the small net polarization occurring from the arrangement of ZnN3F2 trigonal bipyramids. Spectroscopic and thermal characterizations along with calculations for the title materials are reported.

References

Feb 24, 2001·Inorganic Chemistry·M E WelkK R Poeppelmeier
Aug 2, 2001·Journal of the American Chemical Society·P A MaggardK R Poeppelmeier
Oct 16, 2001·Inorganic Chemistry·M E WelkK R Poeppelmeier
Oct 24, 2001·Inorganic Chemistry·Alexander J. NorquistKenneth R. Poeppelmeier
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Sep 29, 2012·Inorganic Chemistry·Romain Gautier, Kenneth R Poeppelmeier
Dec 27, 2016·Journal of the American Chemical Society·T Thao TranP Shiv Halasyamani

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Citations

Jun 25, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Yanjun LiP Shiv Halasyamani
Feb 20, 2020·Chemical Communications : Chem Comm·Minqiang GaiShilie Pan
Oct 10, 2019·Chemistry : a European Journal·Hongil Jo, Kang Min Ok

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