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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.
CFT focuses on...
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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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Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
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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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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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Quantifying the Binding Interactions Between CuII and Peptide Residues in the Presence and Absence of Chromophores
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Exploring and predicting intermolecular binding preferences in crystalline Cu(ii) coordination complexes.

Ivan Kodrin1, Mladen Borovina1, Luka Šmital1

  • 1Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, Zagreb, Croatia. mdjakovic@chem.pmf.hr.

Dalton Transactions (Cambridge, England : 2003)
|October 10, 2019
PubMed
Summary
This summary is machine-generated.

Electrostatic potential models effectively predict supramolecular interactions in copper(II) coordination compounds. Molecular electrostatic potential (MEP) differences guide connectivity, with auxiliary interactions resolving ambiguities in specific cases.

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Area of Science:

  • Coordination Chemistry
  • Supramolecular Chemistry
  • Computational Chemistry

Background:

  • Understanding supramolecular interactions is crucial for designing functional coordination compounds.
  • Predicting the specific assembly of metal-organic complexes remains a challenge.
  • Electrostatic contributions play a significant role in molecular recognition and self-assembly.

Purpose of the Study:

  • To develop a simple electrostatic model for rationalizing supramolecular interactions in Cu(II) coordination compounds.
  • To investigate the predictive power of molecular electrostatic potential (MEP) differences for supramolecular connectivity.
  • To identify factors influencing structural outcomes in ambiguous interaction scenarios.

Main Methods:

  • Synthesis and structural characterization of ten Cu(II) coordination compounds.
  • Utilizing acac-based anions (hexafluoroacetylacetonato, trifluoroacetylacetonato) and pyridine-oxime ligands.
  • Calculation of molecular electrostatic potential (MEP) values at hydrogen-bond acceptor sites.

Main Results:

  • A model based on electrostatic contributions successfully rationalized observed supramolecular interactions.
  • MEP differences at competing hydrogen-bond acceptor sites provided guidelines for predicting supramolecular connectivity.
  • A 'grey zone' was identified where MEP differences were inconclusive, with weak auxiliary interactions determining the final structure.

Conclusions:

  • Simple electrostatic models are effective for predicting supramolecular assembly in Cu(II) coordination complexes.
  • MEP calculations offer valuable insights into controlling supramolecular architecture.
  • Auxiliary interactions are critical for resolving structural ambiguities in the 'grey zone' of electrostatic potential differences.