Alignment of acentric MoO3F33- anions in a polar material: (Ag3MoO3F3)(Ag 3MoO4)Cl

Paul A. Maggard, Tiffany S. Nault, Charlotte L. Stern, Kenneth R. Poeppelmeier*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

403 Scopus citations

Abstract

(Ag3MoO3F3)(Ag3MoO 4)Cl was synthesized by hydro(solvato)thermal methods and characterized by single-crystal X-ray diffraction (P3m1, No. 156, Z=1, a=7.4488(6)Å, c=5.9190(7)Å). The transparent colorless crystals are comprised of chains of distorted fac-MoO3F33- octahedra and MoO42- tetrahedra anions, as suggested by the formulas Ag3MoO3F3 and Ag 3MoO4+, and are connected through Ag + cations in a polar alignment along the c-axis. One Cl- anion per formula unit serves as a charge balance and connects the two types of chains in a staggered fashion, offset by ∼1/2×c. In MoO 42-, the Mo atom displaces towards a single oxide vertex, and in MoO3F33-, the Mo displaces towards the three oxide ligands. The ordered oxide-fluoride ligands on the MoO 3F33- anion is important to prevent local inversion centers, while the polar organization is directed by the Cl - anion and interchain dipole-dipole interactions. The dipole moments of MoO3F33- and MoO4 2- align in the negative c-axis direction, to give a polar structure with no cancellation of the individual moments. The direction and magnitude of the dipole moments for MoO3F33- and MoO 42- were calculated from bond valence analyses and are 6. 1 and 1.9debye (10-18esucm) respectively, compared to 4.4debye for polar NbO6 octahedra in LiNbO3, and 4.5debye for polar TiO6 octahedra in KTiOPO4 (KTP).

Original languageEnglish (US)
Pages (from-to)27-33
Number of pages7
JournalJournal of Solid State Chemistry
Volume175
Issue number1
DOIs
StatePublished - Oct 2003

Funding

The authors gratefully acknowledge support from the National Science Foundation (NSF), Solid State Chemistry, (Award No. DMR-9727516), and made use of the Central Facilities supported by the MRSEC program of the National Science Foundation (Grant DMR-0076097) at the Materials Research Center of Northwestern University. T.S.N. thanks the NSF for summer undergraduate research support as part of the REU program at Northwestern University. The authors also thank Professor Shiv Halasyamani for help with the SHG measurements, and also Professor George Schatz for helpful comments concerning the dipole moment calculations.

Keywords

  • Dipole moment calculation
  • Metal oxyfluoride anions
  • Polar compound

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Ceramics and Composites
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Fingerprint

Dive into the research topics of 'Alignment of acentric MoO3F33- anions in a polar material: (Ag3MoO3F3)(Ag 3MoO4)Cl'. Together they form a unique fingerprint.

Cite this