Resonance enhancement of the Raman-spectrum of bipyridyl gold(iii) chloro complexes

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Abstract

Using exciting wavelengths in the visible region, both bipyridyl Au2Cl6 and bipyridyl AuCl3 are shown to exhibit resonance-enhanced Raman scattering. The enhancement in bipyridyl Au2Cl6 is largest with 488.0 and 514.5 nm excitation, both bipyridyl ring and metal-ligand stretching vibrations are affected to about the same extent. The electronic transitions which give rise to the enhancement are assigned as transitions involving σ molecular orbitals delocalized over the complete molecule. In the resonance profile of bipyridyl AuCl3, there were three peaks at 568.2, 514.4 and below 476 nm and, in addition, there is a probable B term enhancement. In this molecule the resonance arises from transition between more localized molecular orbitals assigned as due to a transition on the gold-nitrogen bond, to π→π* transitions on the bipyridyl ring and the B term to a transition located mainly on the gold-chloride bonds. Some of these enhancements can be correlated with weak structure observed in the 10 K absorption spectrum of the complex.
LanguageEnglish
Pages737-741
Number of pages4
JournalSpectrochimica acta. Part A: Molecular spectroscopy
Volume38
Issue number7
DOIs
Publication statusPublished - 1982

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Raman scattering
Gold
Molecular orbitals
Molecules
Stretching
Absorption spectra
Ligands
Nitrogen
Wavelength
Metals

Keywords

  • wavelengths
  • bipyridyl Au2Cl6
  • bipyridyl AuCl3
  • Raman scattering
  • vibrations
  • molecular orbitals
  • molecule

Cite this

@article{3ea69bcb2a40479d8c56685c92a79202,
title = "Resonance enhancement of the Raman-spectrum of bipyridyl gold(iii) chloro complexes",
abstract = "Using exciting wavelengths in the visible region, both bipyridyl Au2Cl6 and bipyridyl AuCl3 are shown to exhibit resonance-enhanced Raman scattering. The enhancement in bipyridyl Au2Cl6 is largest with 488.0 and 514.5 nm excitation, both bipyridyl ring and metal-ligand stretching vibrations are affected to about the same extent. The electronic transitions which give rise to the enhancement are assigned as transitions involving σ molecular orbitals delocalized over the complete molecule. In the resonance profile of bipyridyl AuCl3, there were three peaks at 568.2, 514.4 and below 476 nm and, in addition, there is a probable B term enhancement. In this molecule the resonance arises from transition between more localized molecular orbitals assigned as due to a transition on the gold-nitrogen bond, to π→π* transitions on the bipyridyl ring and the B term to a transition located mainly on the gold-chloride bonds. Some of these enhancements can be correlated with weak structure observed in the 10 K absorption spectrum of the complex.",
keywords = "wavelengths, bipyridyl Au2Cl6, bipyridyl AuCl3, Raman scattering, vibrations, molecular orbitals, molecule",
author = "A.A. McConnell and D.H. Brown and W.E. Smith",
year = "1982",
doi = "10.1016/0584-8539(82)80060-3",
language = "English",
volume = "38",
pages = "737--741",
journal = "Spectrochimica acta. Part A: Molecular spectroscopy",
issn = "0584-8539",
publisher = "Pergamon Press Ltd.",
number = "7",

}

TY - JOUR

T1 - Resonance enhancement of the Raman-spectrum of bipyridyl gold(iii) chloro complexes

AU - McConnell, A.A.

AU - Brown, D.H.

AU - Smith, W.E.

PY - 1982

Y1 - 1982

N2 - Using exciting wavelengths in the visible region, both bipyridyl Au2Cl6 and bipyridyl AuCl3 are shown to exhibit resonance-enhanced Raman scattering. The enhancement in bipyridyl Au2Cl6 is largest with 488.0 and 514.5 nm excitation, both bipyridyl ring and metal-ligand stretching vibrations are affected to about the same extent. The electronic transitions which give rise to the enhancement are assigned as transitions involving σ molecular orbitals delocalized over the complete molecule. In the resonance profile of bipyridyl AuCl3, there were three peaks at 568.2, 514.4 and below 476 nm and, in addition, there is a probable B term enhancement. In this molecule the resonance arises from transition between more localized molecular orbitals assigned as due to a transition on the gold-nitrogen bond, to π→π* transitions on the bipyridyl ring and the B term to a transition located mainly on the gold-chloride bonds. Some of these enhancements can be correlated with weak structure observed in the 10 K absorption spectrum of the complex.

AB - Using exciting wavelengths in the visible region, both bipyridyl Au2Cl6 and bipyridyl AuCl3 are shown to exhibit resonance-enhanced Raman scattering. The enhancement in bipyridyl Au2Cl6 is largest with 488.0 and 514.5 nm excitation, both bipyridyl ring and metal-ligand stretching vibrations are affected to about the same extent. The electronic transitions which give rise to the enhancement are assigned as transitions involving σ molecular orbitals delocalized over the complete molecule. In the resonance profile of bipyridyl AuCl3, there were three peaks at 568.2, 514.4 and below 476 nm and, in addition, there is a probable B term enhancement. In this molecule the resonance arises from transition between more localized molecular orbitals assigned as due to a transition on the gold-nitrogen bond, to π→π* transitions on the bipyridyl ring and the B term to a transition located mainly on the gold-chloride bonds. Some of these enhancements can be correlated with weak structure observed in the 10 K absorption spectrum of the complex.

KW - wavelengths

KW - bipyridyl Au2Cl6

KW - bipyridyl AuCl3

KW - Raman scattering

KW - vibrations

KW - molecular orbitals

KW - molecule

UR - http://dx.doi.org/10.1016/0584-8539(82)80060-3

U2 - 10.1016/0584-8539(82)80060-3

DO - 10.1016/0584-8539(82)80060-3

M3 - Article

VL - 38

SP - 737

EP - 741

JO - Spectrochimica acta. Part A: Molecular spectroscopy

T2 - Spectrochimica acta. Part A: Molecular spectroscopy

JF - Spectrochimica acta. Part A: Molecular spectroscopy

SN - 0584-8539

IS - 7

ER -