Assisting the Effective Design of Polar Iodates with Early Transition-Metal Oxide Fluoride Anions

Hongwei Yu, Matthew L. Nisbet, Kenneth R Poeppelmeier

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

Polar materials are of great technical interest but challenging to effectively synthesize. That is especially true for iodates, an important class of visible and mid-IR transparent nonlinear optical (NLO) materials. Aiming at developing a new design strategy for polar iodates, we successfully synthesized two sets of polymorphic early transition-metal (ETM) oxide-fluoride iodates, α- and β-Ba[VFO2(IO3)2] and α- and β-Ba2[VO2F2(IO3)2]IO3, based on the distinct structure-directing properties of oxide-fluoride anions. α- and β-Ba[VFO2(IO3)2] contain the trans-[VFO2(IO3)2]2- polyanion and crystallize in the nonpolar space groups Pbcn and P212121. In contrast, α- and β-Ba2[VO2F2(IO3)2]IO3 contain the cis-[VO2F2(IO3)2]3- λ-shaped polyanion and crystallize in the polar space groups Pna21 and P21, respectively. Detailed structural analyses show that the variable polar orientation of trans-[VFO2(IO3)2]2- polyanions is the main cause of the nonpolar structures in α- and β-Ba[VFO2(IO3)2]. However, the λ-shaped configuration of cis-[VO2F2(IO3)2]3- polyanions can effectively guarantee the polar structures. Further property measurements show that polar α- and β-Ba2[VO2F2(IO3)2]IO3 possess excellent NLO properties, including the large SHG responses (∼9 × KDP), wide visible and mid-IR transparent region (∼0.5-10.5 μm), and high thermal stability (up to 470 °C). Therefore, combining cis-directing oxide-fluoride anions and iodates is a viable strategy for the effective design of polar iodates.

Original languageEnglish
Pages (from-to)8868-8876
Number of pages9
JournalJournal of the American Chemical Society
Volume140
Issue number28
DOIs
Publication statusPublished - Jul 18 2018

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Iodates
Fluorides
Oxides
Transition metals
Anions
Negative ions
Metals
Optical materials
Thermodynamic stability
Optical properties
Hot Temperature
polyanions

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Assisting the Effective Design of Polar Iodates with Early Transition-Metal Oxide Fluoride Anions. / Yu, Hongwei; Nisbet, Matthew L.; Poeppelmeier, Kenneth R.

In: Journal of the American Chemical Society, Vol. 140, No. 28, 18.07.2018, p. 8868-8876.

Research output: Contribution to journalArticle

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abstract = "Polar materials are of great technical interest but challenging to effectively synthesize. That is especially true for iodates, an important class of visible and mid-IR transparent nonlinear optical (NLO) materials. Aiming at developing a new design strategy for polar iodates, we successfully synthesized two sets of polymorphic early transition-metal (ETM) oxide-fluoride iodates, α- and β-Ba[VFO2(IO3)2] and α- and β-Ba2[VO2F2(IO3)2]IO3, based on the distinct structure-directing properties of oxide-fluoride anions. α- and β-Ba[VFO2(IO3)2] contain the trans-[VFO2(IO3)2]2- polyanion and crystallize in the nonpolar space groups Pbcn and P212121. In contrast, α- and β-Ba2[VO2F2(IO3)2]IO3 contain the cis-[VO2F2(IO3)2]3- λ-shaped polyanion and crystallize in the polar space groups Pna21 and P21, respectively. Detailed structural analyses show that the variable polar orientation of trans-[VFO2(IO3)2]2- polyanions is the main cause of the nonpolar structures in α- and β-Ba[VFO2(IO3)2]. However, the λ-shaped configuration of cis-[VO2F2(IO3)2]3- polyanions can effectively guarantee the polar structures. Further property measurements show that polar α- and β-Ba2[VO2F2(IO3)2]IO3 possess excellent NLO properties, including the large SHG responses (∼9 × KDP), wide visible and mid-IR transparent region (∼0.5-10.5 μm), and high thermal stability (up to 470 °C). Therefore, combining cis-directing oxide-fluoride anions and iodates is a viable strategy for the effective design of polar iodates.",
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