Cadmium(II) cysteine complexes in the solid state

A multispectroscopic study

Farideh Jalilehvand, Vicky Mah, Bonnie O. Leung, J. Mink, Guy M. Bernard, Laszlo Hajba

Research output: Contribution to journalArticle

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Abstract

Cadmium(II) cysteinate compounds have recently been recognized to provide an environmentally friendly route for the production of CdS nanoparticles, used in semiconductors. In this article, we have studied the coordination for two cadmium(II) cysteinates, Cd(HCys)2 ·H2O(1) and {Cd(HCys)2 ·H2O}2 ·H3G+ClO4- (2), by means of vibrational (Raman and IR absorption), solid-state NMR (113Cd and 13C), and Cd K- and L3-edge X-ray absorption spectroscopy. Indistinguishable Cd K-edge extended X-ray absorption fine structure (EXAFS) and Cd L3-edge X-ray absorption near edge structure (XANES) spectra were obtained for the two compounds, showing similar local structure around the cadmium(II) ions. The vibrational spectra show that the cysteine amine group is protonated (NH3+) and not involved in bonding. The 113Cd solid-state cross-polarization magic angle spinning NMR spectra showed a broad signal in the ∼500-700 ppm range, with the peak maximum at about 650 ppm, indicating three to four coordinated thiolate groups. Careful analyses of low-frequency Raman and far-IR spectra revealed bridging and terminal Cd-S vibrational bands. The average Cd-S distance of 2.52 ± 0.02 A that constantly emerged from least-squares curve-fitting of the EXAFS spectra is consistent with CdS4 and CdS3O coordination. Both structural models yielded reasonable values for the refined parameters, with a slightly better fit for the CdS3O configuration, for which the Cd-O distance of 2.27 ± 0.04 A was obtained. The Cd L3-edge XANES spectra of 1 and 2 resembled that of the CdS3O model compound and showed that the coordination around Cd(II) ions in 1 and 2 cannot be exclusively CdS4. The small separation of 176 cm-1 between the infrared symmetric and antisymmetric COO- stretching modes indicates monodentate or strongly asymmetrical bidentate coordination of a cysteine carboxylate group in the CdS3O units. The combined results are consistent with a "cyclic/cage" type of structure for both the amorphous solids 1 and 2, composed of CdS4 and CdS3O units with single thiolate (Cd-S-Cd) bridges, although a minor amount of cadmium(II) sites with CdS3O2-3 and CdS4O coordination geometries cannot be ruled out.

Original languageEnglish
Pages (from-to)4219-4230
Number of pages12
JournalInorganic Chemistry
Volume48
Issue number9
DOIs
Publication statusPublished - May 4 2009

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cysteine
X ray absorption
Cadmium
cadmium
Cysteine
solid state
Nuclear magnetic resonance
Ions
x rays
Magic angle spinning
X ray absorption spectroscopy
Curve fitting
Vibrational spectra
fine structure
Stretching
Amines
nuclear magnetic resonance
cross polarization
curve fitting
Polarization

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Jalilehvand, F., Mah, V., Leung, B. O., Mink, J., Bernard, G. M., & Hajba, L. (2009). Cadmium(II) cysteine complexes in the solid state: A multispectroscopic study. Inorganic Chemistry, 48(9), 4219-4230. https://doi.org/10.1021/ic900145n

Cadmium(II) cysteine complexes in the solid state : A multispectroscopic study. / Jalilehvand, Farideh; Mah, Vicky; Leung, Bonnie O.; Mink, J.; Bernard, Guy M.; Hajba, Laszlo.

In: Inorganic Chemistry, Vol. 48, No. 9, 04.05.2009, p. 4219-4230.

Research output: Contribution to journalArticle

Jalilehvand, F, Mah, V, Leung, BO, Mink, J, Bernard, GM & Hajba, L 2009, 'Cadmium(II) cysteine complexes in the solid state: A multispectroscopic study', Inorganic Chemistry, vol. 48, no. 9, pp. 4219-4230. https://doi.org/10.1021/ic900145n
Jalilehvand, Farideh ; Mah, Vicky ; Leung, Bonnie O. ; Mink, J. ; Bernard, Guy M. ; Hajba, Laszlo. / Cadmium(II) cysteine complexes in the solid state : A multispectroscopic study. In: Inorganic Chemistry. 2009 ; Vol. 48, No. 9. pp. 4219-4230.
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