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Spectroscopy as a tool to detect multinuclear Cu(II)-triethanolamine complexes in aqueous solution

Petra Lommens (UGent) , Pieter Tack (UGent) , Luce Vander Elst, Isabel Van Driessche (UGent) , Laszlo Vincze (UGent) and Davy Sinnaeve (UGent)
(2018) DALTON TRANSACTIONS. 47(11). p.3755-3763
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Abstract
Complexes of Cu(ii) with triethanolamine (TEA) are widely used in aqueous precursor solutions of Cu-based catalysts and metal oxides such as YBa2Cu3O7- superconductors. An outstanding question is whether such complexes are multinuclear in solution. Here, we use various spectroscopic techniques to unmistakably prove the existence of such multimers. Firstly, we introduce an original approach based on NMR spectroscopy and the Evans method that establishes the existence of multimers in aqueous solution at pH 4 and higher, and allows precise monitoring of the formation of these complexes with increasing pH. Secondly, we use extended X-ray absorption fine structure (EXAFS) spectroscopy to show that a Cu-Cu interaction exists at pH 9.5, which is not observed in acidic (pH 2) solutions. Finally, NMRD measurements reveal additional structural information regarding the multinuclear complexes. Knowledge concerning the nature of Cu(ii)-TEA complexes in solution is of great relevance in view of the design of speciation models to predict the stability of copper triethanolamine-based precursor solutions.
Keywords
PARAMAGNETIC-SUSCEPTIBILITY, TRIETHANOLAMINE COMPLEXES, PEROXIDATIVE, OXIDATION, MAGNETIC-FIELD, EVANS METHOD, RELAXATION, COPPER(II), NMR, SYSTEM, DEPENDENCE

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MLA
Lommens, Petra, et al. “Spectroscopy as a Tool to Detect Multinuclear Cu(II)-Triethanolamine Complexes in Aqueous Solution.” DALTON TRANSACTIONS, vol. 47, no. 11, 2018, pp. 3755–63, doi:10.1039/c7dt04146b.
APA
Lommens, P., Tack, P., Vander Elst, L., Van Driessche, I., Vincze, L., & Sinnaeve, D. (2018). Spectroscopy as a tool to detect multinuclear Cu(II)-triethanolamine complexes in aqueous solution. DALTON TRANSACTIONS, 47(11), 3755–3763. https://doi.org/10.1039/c7dt04146b
Chicago author-date
Lommens, Petra, Pieter Tack, Luce Vander Elst, Isabel Van Driessche, Laszlo Vincze, and Davy Sinnaeve. 2018. “Spectroscopy as a Tool to Detect Multinuclear Cu(II)-Triethanolamine Complexes in Aqueous Solution.” DALTON TRANSACTIONS 47 (11): 3755–63. https://doi.org/10.1039/c7dt04146b.
Chicago author-date (all authors)
Lommens, Petra, Pieter Tack, Luce Vander Elst, Isabel Van Driessche, Laszlo Vincze, and Davy Sinnaeve. 2018. “Spectroscopy as a Tool to Detect Multinuclear Cu(II)-Triethanolamine Complexes in Aqueous Solution.” DALTON TRANSACTIONS 47 (11): 3755–3763. doi:10.1039/c7dt04146b.
Vancouver
1.
Lommens P, Tack P, Vander Elst L, Van Driessche I, Vincze L, Sinnaeve D. Spectroscopy as a tool to detect multinuclear Cu(II)-triethanolamine complexes in aqueous solution. DALTON TRANSACTIONS. 2018;47(11):3755–63.
IEEE
[1]
P. Lommens, P. Tack, L. Vander Elst, I. Van Driessche, L. Vincze, and D. Sinnaeve, “Spectroscopy as a tool to detect multinuclear Cu(II)-triethanolamine complexes in aqueous solution,” DALTON TRANSACTIONS, vol. 47, no. 11, pp. 3755–3763, 2018.
@article{8561213,
  abstract     = {{Complexes of Cu(ii) with triethanolamine (TEA) are widely used in aqueous precursor solutions of Cu-based catalysts and metal oxides such as YBa2Cu3O7- superconductors. An outstanding question is whether such complexes are multinuclear in solution. Here, we use various spectroscopic techniques to unmistakably prove the existence of such multimers. Firstly, we introduce an original approach based on NMR spectroscopy and the Evans method that establishes the existence of multimers in aqueous solution at pH 4 and higher, and allows precise monitoring of the formation of these complexes with increasing pH. Secondly, we use extended X-ray absorption fine structure (EXAFS) spectroscopy to show that a Cu-Cu interaction exists at pH 9.5, which is not observed in acidic (pH 2) solutions. Finally, NMRD measurements reveal additional structural information regarding the multinuclear complexes. Knowledge concerning the nature of Cu(ii)-TEA complexes in solution is of great relevance in view of the design of speciation models to predict the stability of copper triethanolamine-based precursor solutions.}},
  author       = {{Lommens, Petra and Tack, Pieter and Vander Elst, Luce and Van Driessche, Isabel and Vincze, Laszlo and Sinnaeve, Davy}},
  issn         = {{1477-9226}},
  journal      = {{DALTON TRANSACTIONS}},
  keywords     = {{PARAMAGNETIC-SUSCEPTIBILITY,TRIETHANOLAMINE COMPLEXES,PEROXIDATIVE,OXIDATION,MAGNETIC-FIELD,EVANS METHOD,RELAXATION,COPPER(II),NMR,SYSTEM,DEPENDENCE}},
  language     = {{eng}},
  number       = {{11}},
  pages        = {{3755--3763}},
  title        = {{Spectroscopy as a tool to detect multinuclear Cu(II)-triethanolamine complexes in aqueous solution}},
  url          = {{http://doi.org/10.1039/c7dt04146b}},
  volume       = {{47}},
  year         = {{2018}},
}

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