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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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Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
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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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Crystal Field Theory
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Metal ions can be separated from one another by complexation with organic ligands–the chelating agent– to form uncharged chelates. Here, the chelating agent must contain hydrophobic groups and behave as a weak acid, losing a proton to bind with the metal. Since most organic ligands used in this process are insoluble or undergo oxidation in the aqueous phase, the chelating agent is initially added to the organic phase and extracted into the aqueous phase. The metal-ligand complex is...
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Intermetallic Charge Transfer in V-Substituted PbCrO3.

Takahiro Ogata1, Yuki Sakai1,2, Takumi Nishikubo1

  • 1Laboratory for Materials and Structures, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, Kanagawa 226-8503, Japan.

Inorganic Chemistry
|April 27, 2021
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Vanadium substitution in lead chromate (PbCrO3) stabilizes a high-pressure phase at ambient conditions. This research investigates the structural and charge state changes in lead vanadium chromate (PbCr1-xVxO3) compounds.

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Area of Science:

  • Materials Science
  • Solid-State Chemistry
  • Condensed Matter Physics

Background:

  • Lead chromate (PbCrO3) exhibits unique Pb charge disproportionation (Pb2+/Pb4+) at ambient pressure.
  • Pressure application induces charge transfer, leading to a Pb2+Cr4+O3 state and significant volume reduction.

Purpose of the Study:

  • Investigate structural and charge distribution modifications in PbCr1-xVxO3.
  • Determine the effect of vanadium (V) substitution on the PbCrO3 phase stability.

Main Methods:

  • Synthesis and characterization of PbCr1-xVxO3 compounds.
  • High-resolution X-ray diffraction for structural analysis.
  • Hard X-ray photoemission spectroscopy (HAXPES) for charge state determination.

Main Results:

  • A cubic crystal structure was observed for 0 ≤ x ≤ 0.60.
  • A discontinuous unit cell volume reduction occurred between x = 0.35 and 0.40.
  • HAXPES confirmed a transition from mixed Pb2+/Pb4+ to solely Pb2+ at x = 0.40, stabilizing the high-pressure cubic phase.

Conclusions:

  • Vanadium substitution effectively stabilizes the high-pressure Pb2+Cr4+O3-type cubic phase at ambient conditions.
  • A polar tetragonal phase of the PbVO3 type emerges with further V substitution (x = 0.80).
  • This study provides insights into tuning the electronic and structural properties of perovskite oxides through aliovalent substitution.