Affordable Access

Vibronic luminescence properties of tetragonal transition metal complexes

McGill University
Publication Date
  • Chemistry
  • Physical.
  • Mathematics


The luminescence properties of trans-dioxo rhenium(V) and osmium(VI) [d2] and square-planar platinum(II) and palladium(II) [d8] transition metal complexes have been studied as a function of temperature and pressure. Both types of complexes studied have idealized D4h point group symmetry with the d2 systems representing the tetragonally compressed limit of a six-coordinate complex in the D4h point group and the d8 systems representing the tetragonally elongated limit. The observed luminescence in both classes of complexes has been assigned as a metal-centered (d → d) 3Eg → 1A1g transition. The application of external pressure provides a means to induce minor changes in the molecular geometries of these model systems that reveal the delicate interplay between structural and electronic properties. Pressure-dependent spectroscopic data are analyzed quantitatively using theoretical models adapted from high-resolution low-temperature spectra where emitting state displacements along vibrational coordinates are determined from resolved vibronic structure. These combined experimental and theoretical techniques allow for a full characterization of the ground and emitting state potential energy surfaces and their explicit dependence on structural parameters.

There are no comments yet on this publication. Be the first to share your thoughts.