skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: X-ray-Excited Optical Luminescence (XEOL) and X-ray Absorption Fine Structures (XAFS) Studies of Gold(I) Complexes with Diphosphine and Bipyridine Ligands

Abstract

Synchrotron techniques, X-ray-excited optical luminescence (XEOL) combined with X-ray absorption fine structures (XAFS), have been used to study the electronic structure and optical properties of a series of luminescent gold(I) complexes with diphosphine and bipyridine ligands using tunable X-rays (in the regions of the C and P K-edges and the Au L{sub 3}-edge) and UV from synchrotron light sources. The effects of gold-ligand and aurophilic interactions on the luminescence from these gold(I) complexes have been investigated. It is found that the luminescence from these complexes is phosphorescence, primarily due to the decay of the Au (5d) {yields} PR{sub 3} ({pi}*), metal to ligand charge transfer (MLCT) excitation as well as contributions from the conjugated {pi}-system in the bipyridine ligands via the gold-nitrogen bond. The large Au 5d spin-orbit coupling enhances the intersystem crossing. The elongation of the hydrocarbon chain of the diphosphine ligand does not greatly affect the spectral features of the luminescence from the gold(I) complexes. However, the intensity of the luminescence was reduced significantly when the bipyridine ligand was replaced with 1,2-bis(4-pyridylamido)benzene. The aurophilic interaction, as investigated by EXAFS at the Au L{sub 3}-edge, is shown to be only one of the factors that contribute to the luminescencemore » of the complexes.« less

Authors:
; ; ; ; ;  [1]
  1. CLS
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE
OSTI Identifier:
1007563
Resource Type:
Journal Article
Journal Name:
Inorg. Chem.
Additional Journal Information:
Journal Volume: 46; Journal Issue: (3) ; 02, 2007; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
ENGLISH
Subject:
43 PARTICLE ACCELERATORS; ABSORPTION; BIPYRIDINES; CHAINS; DECAY; ELECTRONIC STRUCTURE; ELONGATION; EXCITATION; FINE STRUCTURE; HYDROCARBONS; LIGHT SOURCES; LUMINESCENCE; OPTICAL PROPERTIES; PHOSPHORESCENCE; SYNCHROTRONS

Citation Formats

Kim, Pil-Sook G, Hu, Yongfeng, Brandys, Marie-C, Burchell, Tara J, Puddephatt, Richard J, Sham, Tsun K, and UWO). X-ray-Excited Optical Luminescence (XEOL) and X-ray Absorption Fine Structures (XAFS) Studies of Gold(I) Complexes with Diphosphine and Bipyridine Ligands. United States: N. p., 2008. Web. doi:10.1021/ic0609352.
Kim, Pil-Sook G, Hu, Yongfeng, Brandys, Marie-C, Burchell, Tara J, Puddephatt, Richard J, Sham, Tsun K, & UWO). X-ray-Excited Optical Luminescence (XEOL) and X-ray Absorption Fine Structures (XAFS) Studies of Gold(I) Complexes with Diphosphine and Bipyridine Ligands. United States. doi:10.1021/ic0609352.
Kim, Pil-Sook G, Hu, Yongfeng, Brandys, Marie-C, Burchell, Tara J, Puddephatt, Richard J, Sham, Tsun K, and UWO). Tue . "X-ray-Excited Optical Luminescence (XEOL) and X-ray Absorption Fine Structures (XAFS) Studies of Gold(I) Complexes with Diphosphine and Bipyridine Ligands". United States. doi:10.1021/ic0609352.
@article{osti_1007563,
title = {X-ray-Excited Optical Luminescence (XEOL) and X-ray Absorption Fine Structures (XAFS) Studies of Gold(I) Complexes with Diphosphine and Bipyridine Ligands},
author = {Kim, Pil-Sook G and Hu, Yongfeng and Brandys, Marie-C and Burchell, Tara J and Puddephatt, Richard J and Sham, Tsun K and UWO)},
abstractNote = {Synchrotron techniques, X-ray-excited optical luminescence (XEOL) combined with X-ray absorption fine structures (XAFS), have been used to study the electronic structure and optical properties of a series of luminescent gold(I) complexes with diphosphine and bipyridine ligands using tunable X-rays (in the regions of the C and P K-edges and the Au L{sub 3}-edge) and UV from synchrotron light sources. The effects of gold-ligand and aurophilic interactions on the luminescence from these gold(I) complexes have been investigated. It is found that the luminescence from these complexes is phosphorescence, primarily due to the decay of the Au (5d) {yields} PR{sub 3} ({pi}*), metal to ligand charge transfer (MLCT) excitation as well as contributions from the conjugated {pi}-system in the bipyridine ligands via the gold-nitrogen bond. The large Au 5d spin-orbit coupling enhances the intersystem crossing. The elongation of the hydrocarbon chain of the diphosphine ligand does not greatly affect the spectral features of the luminescence from the gold(I) complexes. However, the intensity of the luminescence was reduced significantly when the bipyridine ligand was replaced with 1,2-bis(4-pyridylamido)benzene. The aurophilic interaction, as investigated by EXAFS at the Au L{sub 3}-edge, is shown to be only one of the factors that contribute to the luminescence of the complexes.},
doi = {10.1021/ic0609352},
journal = {Inorg. Chem.},
issn = {0020-1669},
number = (3) ; 02, 2007,
volume = 46,
place = {United States},
year = {2008},
month = {10}
}