Pressure-Induced Change of d-d Luminescence Energies, Vibronic Structure, and Band Intensities in Transition Metal Complexes

Abstract

The effects of hydrostatic pressure on the luminescence spectra of tetragonal transition metal complexes with nondegenerate electronic ground states are analyzed quantitatively using models based on potential energy surfaces defined along normal coordinates. Pressure-induced changes of intensity distributions within vibronic progressions, band maxima, electronic origins and relaxation rates are discussed for metal-oxo complexes of rhenium(V) and molybdenum(IV) (d 2 electron configuration) and for square-planar complexes of palladium(II) and platinum(II) (d 8 electron configuration).

Variation of M···H–C Interactions in Square-Planar Complexes of Nickel(II), Palladium(II), and Platinum(II) Probed by Luminescence Spectroscopy and X-ray Diffraction at Variable Pressure

“…Variable-pressure studies provide quantitative, continuously varied spectroscopic properties of crystalline complexes, [9][10][11] and are especially attractive to probe structure-energy relations. [12][13][14][15] Only rarely have such continuous variations been explored by any spectroscopic technique for isoelectronic complexes with different metal centers. In this report, we compare variable-pressure luminescence spectra of structurally similar d 8 complexes with identical ligands, but different metal centers to quantify luminescence energy variations.…”