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Ionic Crystal Structures02:42

Ionic Crystal Structures

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Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
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If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
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Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
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Valence Bond Theory02:42

Valence Bond Theory

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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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Ionic Bonding and Electron Transfer02:48

Ionic Bonding and Electron Transfer

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Ions are atoms or molecules bearing an electrical charge. A cation (a positive ion) forms when a neutral atom loses one or more electrons from its valence shell, and an anion (a negative ion) forms when a neutral atom gains one or more electrons in its valence shell. Compounds composed of ions are called ionic compounds (or salts), and their constituent ions are held together by ionic bonds: electrostatic forces of attraction between oppositely charged cations and anions. 
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Chirality at Nitrogen, Phosphorus, and Sulfur02:30

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Chirality is most prevalent in carbon-based tetrahedral compounds, but this important facet of molecular symmetry extends to sp3-hybridized nitrogen, phosphorus and sulfur centers, including trivalent molecules with lone pairs. Here, the lone pair behaves as a functional group in addition to the other three substituents to form an analogous tetrahedral center that can be chiral.
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
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Updated: May 22, 2025

Sputter Growth and Characterization of Metamagnetic B2-ordered FeRh Epilayers
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Revealed Preferential Short-Range Anion Ordering in Disordered RbM2O5F (M = Nb, Ta) Pyrochlore-Type Oxyfluorides.

Ouail Zakary1, Monique Body1, Vincent Sarou-Kanian2

  • 1Institut des Molécules et Matériaux du Mans (IMMM)─UMR 6283 CNRS, Le Mans Université, Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France.

Inorganic Chemistry
|March 12, 2025
PubMed
Summary

We studied RbM2O5F (M = Nb, Ta) pyrochlore-type oxyfluorides, revealing short-range anion ordering. This finding is crucial for understanding disordered materials and designing functional materials.

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Area of Science:

  • Materials Science
  • Solid-State Chemistry
  • Crystallography

Background:

  • Disordered materials with mixed-occupancy sites are key for tuning physicochemical properties.
  • Understanding crystal structures is essential for designing functional materials.

Purpose of the Study:

  • Investigate the crystal structure of RbM2O5F (M = Nb, Ta) pyrochlore-type oxyfluorides.
  • Clarify the distribution of oxygen and fluorine anions and Rb occupancy.
  • Determine if short-range anion ordering exists in these materials.

Main Methods:

  • Multimodal approach combining experimental and computational techniques.
  • Rietveld structural refinement of powder X-ray powder diffraction (PXRD) data.
  • Solid-state Nuclear Magnetic Resonance (NMR) spectroscopy (19F MAS, 87Rb and 93Nb (CT)MAS and 3QMAS).
  • Density Functional Theory (DFT) calculations using the supercell approach and PAW/GIPAW methods.

Main Results:

  • RbM2O5F (M = Nb, Ta) oxyfluorides are isostructural with disordered average crystal structures.
  • The anionic site is co-occupied by O and F, and the Rb site is 25% occupied.
  • Experimental and computed NMR parameters indicate distributed local environments.
  • DFT models best matching experimental NMR data reveal preferential short-range anion ordering.

Conclusions:

  • RbM2O5F pyrochlores exhibit preferential short-range anion ordering, not random distribution.
  • The identified ordered structures involve specific arrangements of [MO5F] octahedra and Rb-centered cages.
  • This detailed structural understanding is vital for the rational design of novel oxyfluoride materials.