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Noncentrosymmetry in Mixed Metal Oxide-Fluorides, Can We Control It?

Published online by Cambridge University Press:  01 February 2011

Rachelle Ann F. Pinlac
Affiliation:
r-pinlac@u.northwestern.edu, Northwestern University, Chemistry, Evanston, Illinois, United States
Michael R. Marvel
Affiliation:
mikemarv481@gmail.com, Aurora University, Chemistry, Aurora, Illinois, United States
Julien J.-M. Lesage
Affiliation:
j-lesage@northwestern.edu, Northwestern University, Chemistry, Evanston, Illinois, United States
Kenneth R. Poeppelmeier
Affiliation:
krp@northwestern.edu, Northwestern University, Chemistry, Evanston, Illinois, United States
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Abstract

The rational design of crystal structures, in particular noncentrosymmetric materials, and how to differentiate polar, polar-chiral, and chiral structures, is an ongoing theme in crystal engineering. In KNaNbOF5, the combination of a second-order Jahn Teller active d0 transition metal oxyfluoride anionic unit and mixed K/Na cation coordination environments are shown to result in a polar structure (space group Pna21). The crystal structure analysis of the Na/K-O/F interactions reveals that the potassium cations form one of the two contacts to the under-bonded oxide ions. These interactions satisfy the expected bond valence sums and Pauling's second crystal rule (PSCR), leading to O/F ordering and acentric packing of the [NbOF5]2− anionic unit.

Type
Research Article
Copyright
Copyright © Materials Research Society 2009

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