Spectrum-Structure Correlations in Hexacoordinated Transition Metal Complexes

  • T. Schönherr
Conference paper


To understand the photophysical and photochemical processes a comprehensive knowledge of the molecular energy level scheme is required. It has been found in recent years that even slight changes of the geometric structure can significantly alter the electronic properties of transition metal complexes. This has led to a growing interest in the study of spectrum-structure correlations, in particular for chromium(III) compounds which are of current interest as possible candidates for luminescent solar concentrators (1). In the first section of this paper the potential of common ligand field theory (LFT) will be illustrated to describe trigonal distortions for complexes near to high symmetry. For the properties considered the hexaamminechrornate(III) ion represents an ideal system for the global parametrization within the LFT which is reflected by the high molecular symmetry and the absence of metal-ligand π-bonding. The angular overlap model (AOM), on the other hand, is based on an additive description of metal-ligand interactions using local bonding parameters of σ- and π-type which are more adequate to the chemical way of thinking. One of its advantages over the LFT is that it is easier to include the molecular geometry into energy level calculations, since the AOM parameters are independent of angular distortions within the coordination sphere (2). In the case of osmium(IV) complexes a great deal of information about electronic and geometric structure can be derived from detailed studies of intraconfigurational transitions, and model parameters are given here for the first time. In order to explain spectroscopic properties of transition group metal acetylacetonates an extended AOM is required. Directional π-bonding effects resulting from the phase coupling of chelate molecular orbitals lead to non-additive contributions to the d-orbital energies. We will give an illustration of this type of study below.


Phase Coupling Angular Distortion Energy Level Scheme Bite Angle Ligand Field Theory 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. (1).
    Reisfeld, R. Mater. Sci. Eng. 1985, 71, 375CrossRefGoogle Scholar
  2. (2).
    Hoggard, P.E. Coord. Chem. Rev. 1986, 70, 85CrossRefGoogle Scholar
  3. (3).
    Urushiyama, A.; Schönherr, T.; Schmidtke, H.-H. Ber. Bunsenges. Phys. Chem. 1986, 90, 1195Google Scholar
  4. (4).
    Schoenen, N.; Schmidtke, H.-H. Mol. Phys. 1986, 57, 983CrossRefGoogle Scholar
  5. (5).
    Dorain, P.B.; Patterson, H.H.; Jordan, P.C. J.Chem. Phys.1968, 3845Google Scholar
  6. (6).
    Schönherr, T.; Wernicke, R.; Schmidtke, H.-H. Spectrochim. Acta 1982, 28A, 679 Google Scholar
  7. (7).
    Kozikowski, B.A.; Keiderling, T.A. J. Chem. Phys. 1983, 87, 4630CrossRefGoogle Scholar
  8. (8).
    Homborg, H.; Preetz, W.; Schätzel, G. Z.Naturforsch. 1980,35b,554Google Scholar
  9. (9).
    Strand, D. unpublished resultsGoogle Scholar
  10. (10).
    Schönherr, T., Linder, R.; Eyring, G. Z. Naturforsch. 1983,38a,736Google Scholar
  11. (11).
    Atanasov, M.;Schönherr, T.; Schmidtke, H.-H. Theor. Chim. Acta, in pressGoogle Scholar
  12. (12).
    Ceuleman, A.; Dendooven, M.; Vanquickenborne, L.G. Inorg. Chem. 1985, 24, 1153CrossRefGoogle Scholar
  13. (13).
    Schönherr, T.; Atanasov, M.; Schmidtke, H.-H. Inorg. Chim. Acta, submittedGoogle Scholar

Copyright information

© Springer-Verlag Berlin · Heidelberg 1987

Authors and Affiliations

  • T. Schönherr
    • 1
  1. 1.Institut für Theoretische ChemieUniversität DüsseldorfDüsseldorf 1Germany

Personalised recommendations