Labile degree of disorder in bismuth-oxophosphate compounds: Illustration through three new structural types

Tutkimustuotos: Lehtiartikkeli

Tutkijat

  • A. Aliev
  • D. Endara
  • M. Huvé
  • M. Colmont
  • P. Roussel
  • L. Delevoye
  • T. T. Tran
  • P. S. Halasyamani
  • O. Mentré

Organisaatiot

  • University of Houston
  • Université Lille Nord de France

Kuvaus

Here, we analyze the crystal structures of three new Bi/M oxophosphates, focusing on the ambiguity between order and disorder in different structural subunits. The three structures are original but systematically built on the assembly of O(Bi,M)4 tetrahedra into various 1D-oxocenterd units, separated by PO4 groups that create cationic channels. Two main subunits show versatile degrees of disorder, i.e., the cationic channels and some of the terminal O(Bi,M)4 entities. (a) In the compound [Bi 2(Bi1.56K0.44)disO 3]K0.88dis(PO4)2, the K/K and K/Bi disorder is total on both nano- and micro-sized domains. (b) In the incommensurately modulated [Bi10(Bi∼0.5Cd ∼0.5)8disO16](Bi 0.6Cd0.8)2ord(PO4) 8, only the cationic channels show an ordered Bi/Cd arrangement which can be modified by minor stoichiometric changes between domains. (c) In [Bi18Zn10O21]ordZn5 ord(PO4)14, both subunits are almost perfectly ordered (complex Bi/Zn sequence) into a 7-fold supercell, but this order strongly depends on the observation scale and is mainly lost in micronic-grains also due to slight compositional changes. However, the refined noncentrosymmetric organization is maintained (SHG tests) in the bulk. The relative stability of ordered versus disordered sites is discussed on the basis of the existence of two possible mixed sites and probably depends on the M chemical nature. Disorder was characterized by use of solid-state 31P NMR probing for the first two cases. Finally, the observed disordered or long periodicities along the infinite dimension suggest the sketch of a periodic/rigid skeleton of O(Bi,M)4 units with counterions filling the interspace in more or less disordered arrangements.

Yksityiskohdat

AlkuperäiskieliEnglanti
Sivut861-871
Sivumäärä11
JulkaisuInorganic Chemistry
Vuosikerta53
Numero2
TilaJulkaistu - 21 tammikuuta 2014
OKM-julkaisutyyppiA1 Julkaistu artikkeli, soviteltu

ID: 9394143