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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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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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In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
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Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
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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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The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
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Intervalence Charge Transfer in Nonbonding, Mixed-Valence, Homobimetallic Ytterbium Complexes.

Michael D Roy1, Thaige P Gompa1, Samuel M Greer2

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|February 19, 2024
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Summary

Researchers synthesized a mixed-valence ytterbium complex with a short Yb-Yb distance, demonstrating the first intervalence charge transfer (IVCT) in a molecular lanthanide system. This finding opens new avenues for tuning electronic structures in mixed-oxidation state lanthanide compounds.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Quantum Chemistry

Background:

  • Lanthanide complexes with multiple oxidation states are rare.
  • Intervalence charge transfer (IVCT) is seldom observed in molecular lanthanide systems, typically limited to extended solids.
  • Short lanthanide-lanthanide (Ln-Ln) distances have been reported, often attributed to 5d orbital interactions.

Purpose of the Study:

  • To synthesize and characterize novel ytterbium complexes.
  • To investigate the electronic structure and bonding in mixed-valence lanthanide systems.
  • To observe and analyze intervalence charge transfer (IVCT) in a molecular lanthanide complex.

Main Methods:

  • Synthesis of ytterbium complexes.
  • Characterization using spectroscopic and crystallographic techniques.
  • Computational analysis of electronic structure and bonding.

Main Results:

  • A mixed-valence Yb2^5+ complex was synthesized with a short Yb-Yb distance (2.9507(8) Å).
  • The complex exhibits clear localization of Yb2+ and Yb3+ character.
  • An intervalence charge transfer (IVCT) transition was observed in the visible spectrum, the first for a molecular lanthanide system.

Conclusions:

  • The study demonstrates the ability to tune the electronic structure of mixed-oxidation state lanthanide complexes.
  • High exchange stabilization of the Yb2+ (4f14) configuration disfavors 5d1 bonding.
  • Short metal-metal distances enforced by the ligand framework enable the observation of lanthanide IVCT in molecular systems.