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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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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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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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Crystal Field Theory
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Aurophilic Interactions in Three-Coordinate Gold(I) Complexes with C‑Clamp-like Structures.

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ACS Omega
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Summary

New gold(I) complexes with bridging diphosphines were synthesized. These compounds exhibit unique c-clamp structures and aurophilic interactions but do not display luminescence, differing from typical two-coordinate gold complexes.

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Area of Science:

  • Inorganic Chemistry
  • Coordination Chemistry
  • Materials Science

Background:

  • Aurophilic interactions in gold(I) complexes often lead to luminescence.
  • Three-coordinate gold(I) complexes are less explored compared to two-coordinate counterparts.
  • Bridging diphosphines are key ligands for constructing polynuclear gold complexes.

Purpose of the Study:

  • To synthesize and characterize novel three-coordinate gold(I) complexes.
  • To investigate the structural and photophysical properties of these complexes.
  • To explore the role of bridging diphosphines in mediating aurophilic interactions.

Main Methods:

  • One-pot synthesis involving bridging diphosphines (bis-(diphenylphosphino)-methane or 1,2-bis-(diphenylphosphino)-ethane) and gold(I) precursors.
  • Crystallization to obtain single crystals of the target complexes.
  • X-ray diffraction analysis to determine the molecular structure and gold-gold bond lengths.
  • Photoluminescence spectroscopy at room temperature and low temperature (90 K).

Main Results:

  • Synthesis of two novel gold(I) complexes: [(μ-dppm)-{Au-(bipy)}2]-(PF6)2 and [(μ-dppe)-{Au-(bipy)}2]-(BF4)2.
  • The complexes feature c-clamp-like structures with significant aurophilic interactions (Au-Au distances of 3.0903(6) Å and 3.249(1) Å).
  • Neither complex exhibited luminescence at room temperature or 90 K, contrary to expectations for similar gold(I) systems.

Conclusions:

  • Bridging diphosphines can effectively stabilize three-coordinate gold(I) centers with aurophilic interactions.
  • The observed c-clamp structure and non-luminescent nature highlight unique properties of these three-coordinate gold complexes.
  • The lack of luminescence suggests that the specific coordination environment and bridging ligand influence photophysical behavior.