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Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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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.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
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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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Complexation Equilibria: The Chelate Effect01:19

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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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Complexation Equilibria: Factors Influencing Stability of Complexes01:09

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In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
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Coordination Compounds and Nomenclature02:54

Coordination Compounds and Nomenclature

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In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
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Open for Bismuth: Main Group Metal-to-Ligand Charge Transfer.

Laura A Maurer1, Orion M Pearce1, Franklin D R Maharaj1

  • 1Department of Chemistry, University of Colorado Boulder, Boulder, Colorado 80309, United States.

Inorganic Chemistry
|June 28, 2021
PubMed
Summary

Researchers synthesized bismuth coordination complexes with unique electronic structures. These complexes exhibit optoelectronic properties similar to lead perovskites, offering potential for new electronic applications.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Photophysics

Background:

  • Bismuth (Bi3+) complexes are explored for optoelectronic applications.
  • Understanding hypercoordination in bismuth is crucial for tuning electronic properties.

Purpose of the Study:

  • Synthesize and characterize 4- and 6-coordinate Bi3+ complexes.
  • Investigate the photophysical properties and electronic structure of these complexes.
  • Explore their potential as alternatives to lead-based materials.

Main Methods:

  • Synthesis of Bi(bzq)3 and [Bi(bzq)2]Br using organobismuth precursors.
  • Characterization via absorption spectroscopy and electrochemistry.
  • Density Functional Theory (DFT) calculations to analyze electronic structure.

Main Results:

  • Bi(bzq)3 exhibits significant Bi 6s character in its HOMO due to covalent interactions.
  • Broad emission at 520 nm upon excitation at 450 nm, attributed to MLCT and phosphorescence.
  • The excited state has a 35 μs lifetime, sensitive to oxygen quenching.

Conclusions:

  • Hypercoordination in bismuth complexes can yield desirable optoelectronic properties.
  • Covalent organobismuth interactions mimic the electronic structure of lead perovskites.
  • These findings suggest Bi3+ complexes as promising candidates for optoelectronic devices.