Format

Send to

Choose Destination
See comment in PubMed Commons below
J Am Chem Soc. 2003 Nov 26;125(47):14228-9.

Jahn-Teller distortion in the phosphorescent excited state of three-coordinate Au(I) phosphine complexes.

Author information

1
Department of Chemistry, University of North Texas, Denton, TX 76203-5070, USA.

Abstract

DFT calculations were used to optimize the phosphorescent excited state of three-coordinate [Au(PR3)3]+ complexes. The results indicate that the complexes rearrange from their singlet ground-state trigonal planar geometry to a T-shape in the lowest triplet luminescent excited state. The optimized structure of the exciton contradicts the structure predicted based on the AuP bonding properties of the ground-state HOMO and LUMO. The rearrangement to T-shape is a Jahn-Teller distortion because an electron is taken from the degenerate e' (5dxy, 5dx2-y2) orbital upon photoexcitation of the ground-state D3h complex. The calculated UV absorption and visible emission energies are consistent with the experimental data and explain the large Stokes' shifts while such correlations are not possible in optimized models that constrained the exciton to the ground-state trigonal geometry.

PMID:
14624542
DOI:
10.1021/ja036508u
PubMed Commons home

PubMed Commons

0 comments
How to join PubMed Commons

    Supplemental Content

    Full text links

    Icon for American Chemical Society
    Loading ...
    Support Center