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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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Color in Coordination Complexes
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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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For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
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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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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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Tetra- and hexanuclear string complexes of the coinage metals.

Milena Dahlen1, Tim P Seifert1, Sergei Lebedkin2

  • 1Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstr. 15, Karlsruhe 76131, Germany. roesky@kit.edu.

Chemical Communications (Cambridge, England)
|November 22, 2021
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New coinage metal complexes with a metal string conformation were synthesized. Their photoluminescence properties depend on metal composition, with some showing nearly 100% efficiency below 100 K.

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Area of Science:

  • Coordination Chemistry
  • Organometallic Chemistry
  • Photophysics

Background:

  • The PNNP ligand system, N,N'-bis[(2-diphenylphosphino)phenyl]formamidinate (dpfam), offers versatile coordination possibilities.
  • Coinage metals (gold, copper, silver) are crucial in catalysis and materials science.

Purpose of the Study:

  • To synthesize novel tetranuclear and hexanuclear coinage metal complexes using the dpfam ligand.
  • To investigate the structural and photophysical properties of these complexes.

Main Methods:

  • Synthesis of homo- and heterometallic complexes via reactions with gold, copper, and silver precursors.
  • Structural characterization of the resulting metal string complexes.
  • Photoluminescence (PL) spectroscopy at variable temperatures.

Main Results:

  • Formation of tetranuclear homo- and heterometallic complexes, and a hexanuclear gold complex.
  • All synthesized complexes adopt a metal string conformation.
  • Photoluminescence efficiency is highly dependent on the metal composition.
  • Three compounds exhibit nearly 100% PL efficiency at temperatures below 100 K.

Conclusions:

  • The dpfam ligand facilitates the formation of unique metal string architectures with coinage metals.
  • The photophysical behavior of these complexes can be tuned by varying the metal composition.
  • These findings open avenues for developing new luminescent materials.