Jahn - Teller Distortion in the Phosphorescent Excited State of Three-Coordinate Au(I) Phosphine Complexes

Description:

This article discusses three-coordinate Au(I) phosphine complexes.

Creator(s):
Creation Date: November 4, 2003
Partner(s):
UNT College of Arts and Sciences
Collection(s):
UNT Scholarly Works
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Creator (Author):
Barakat, Khaldoon A.

University of North Texas

Creator (Author):
Cundari, Thomas R., 1964-

University of North Texas

Creator (Author):
Omary, Mohammad A.

University of North Texas

Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, DC]
Date(s):
  • Creation: November 4, 2003
Description:

This article discusses three-coordinate Au(I) phosphine complexes.

Degree:
Department: Chemistry
Note:

Reprinted with permission from the Journal of the American Chemical Society. Copyright 2003 American Chemical Society.

Note:

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.

Physical Description:

2 p.

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Subject(s):
Keyword(s): phosphine complexes | transition metal complexes
Source: Journal of the American Chemical Society, 2003, Washington DC: American Chemical Society, pp. 14228-14229
Partner:
UNT College of Arts and Sciences
Collection:
UNT Scholarly Works
Identifier:
  • DOI: 10.1021/ja036508u
  • ARK: ark:/67531/metadc77134
Resource Type: Article
Format: Text
Rights:
Access: Public
Citation:
Publication Title: Journal of the American Chemical Society
Volume: 125
Issue: 47
Page Start: 14228
Page End: 14229
Peer Reviewed: Yes