The solvation and electrochemical behavior of copper acetylacetonate complexes in ionic liquids

Patrique Nunes, N. Nagy, Elisabete C B A Alegria, Armando J L Pombeiro, Isabel Correia

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

The behavior of copper(II) complexes of pentane-2,4-dione and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, [Cu(acac)2] (1) and [Cu(HFacac)2(H2O)] (2), in ionic liquids and molecular organic solvents, was studied by spectroscopic and electrochemical techniques. The electron paramagnetic resonance characterization (EPR) showed well-resolved spectra in most solvents. In general the EPR spectra of [Cu(acac)2] show higher gz values and lower hyperfine coupling constants, A z, in ionic liquids than in organic solvents, in agreement with longer CuO bond lengths and higher electron charge in the copper ion in the ionic liquids, suggesting coordination of the ionic liquid anions. For [Cu(HFacac)2(H2O)] the opposite was observed suggesting that in ionic liquids there is no coordination of the anions and that the complex is tetrahedrically distorted. The redox properties of the Cu(II) complexes were investigated by cyclic voltammetry (CV) at a Pt electrode (d = 1 mm), in bmimBF4 and bmimNTf2 ionic liquids and, for comparative purposes, in neat organic solvents. The neutral copper(II) complexes undergo irreversible reductions to Cu(I) and Cu(0) species in both ILs and common organic solvents (CH2Cl2 or acetonitrile), but, in ILs, they are usually more easier to reduce (less cathodic reduction potential) than in the organic solvents. Moreover, 1 and 2 are easier to reduce in bmimNTf2 than in bmimBF4 ionic liquid.

Original languageEnglish
Pages (from-to)142-149
Number of pages8
JournalJournal of Molecular Structure
Volume1060
Issue number1
DOIs
Publication statusPublished - Feb 24 2014

Fingerprint

Ionic Liquids
Solvation
Organic solvents
Copper
Anions
Paramagnetic resonance
Bond length
acetyl acetonate
Cyclic voltammetry
Ions
Electrodes
Electrons

Keywords

  • Copper complexes
  • EPR
  • Ionic liquids
  • Solvation
  • Voltammetry

ASJC Scopus subject areas

  • Spectroscopy
  • Analytical Chemistry
  • Inorganic Chemistry
  • Organic Chemistry

Cite this

The solvation and electrochemical behavior of copper acetylacetonate complexes in ionic liquids. / Nunes, Patrique; Nagy, N.; Alegria, Elisabete C B A; Pombeiro, Armando J L; Correia, Isabel.

In: Journal of Molecular Structure, Vol. 1060, No. 1, 24.02.2014, p. 142-149.

Research output: Contribution to journalArticle

Nunes, Patrique ; Nagy, N. ; Alegria, Elisabete C B A ; Pombeiro, Armando J L ; Correia, Isabel. / The solvation and electrochemical behavior of copper acetylacetonate complexes in ionic liquids. In: Journal of Molecular Structure. 2014 ; Vol. 1060, No. 1. pp. 142-149.
@article{79424e5d96ac4134b28bb542fc4dcb93,
title = "The solvation and electrochemical behavior of copper acetylacetonate complexes in ionic liquids",
abstract = "The behavior of copper(II) complexes of pentane-2,4-dione and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, [Cu(acac)2] (1) and [Cu(HFacac)2(H2O)] (2), in ionic liquids and molecular organic solvents, was studied by spectroscopic and electrochemical techniques. The electron paramagnetic resonance characterization (EPR) showed well-resolved spectra in most solvents. In general the EPR spectra of [Cu(acac)2] show higher gz values and lower hyperfine coupling constants, A z, in ionic liquids than in organic solvents, in agreement with longer CuO bond lengths and higher electron charge in the copper ion in the ionic liquids, suggesting coordination of the ionic liquid anions. For [Cu(HFacac)2(H2O)] the opposite was observed suggesting that in ionic liquids there is no coordination of the anions and that the complex is tetrahedrically distorted. The redox properties of the Cu(II) complexes were investigated by cyclic voltammetry (CV) at a Pt electrode (d = 1 mm), in bmimBF4 and bmimNTf2 ionic liquids and, for comparative purposes, in neat organic solvents. The neutral copper(II) complexes undergo irreversible reductions to Cu(I) and Cu(0) species in both ILs and common organic solvents (CH2Cl2 or acetonitrile), but, in ILs, they are usually more easier to reduce (less cathodic reduction potential) than in the organic solvents. Moreover, 1 and 2 are easier to reduce in bmimNTf2 than in bmimBF4 ionic liquid.",
keywords = "Copper complexes, EPR, Ionic liquids, Solvation, Voltammetry",
author = "Patrique Nunes and N. Nagy and Alegria, {Elisabete C B A} and Pombeiro, {Armando J L} and Isabel Correia",
year = "2014",
month = "2",
day = "24",
doi = "10.1016/j.molstruc.2013.12.025",
language = "English",
volume = "1060",
pages = "142--149",
journal = "Journal of Molecular Structure",
issn = "0022-2860",
publisher = "Elsevier",
number = "1",

}

TY - JOUR

T1 - The solvation and electrochemical behavior of copper acetylacetonate complexes in ionic liquids

AU - Nunes, Patrique

AU - Nagy, N.

AU - Alegria, Elisabete C B A

AU - Pombeiro, Armando J L

AU - Correia, Isabel

PY - 2014/2/24

Y1 - 2014/2/24

N2 - The behavior of copper(II) complexes of pentane-2,4-dione and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, [Cu(acac)2] (1) and [Cu(HFacac)2(H2O)] (2), in ionic liquids and molecular organic solvents, was studied by spectroscopic and electrochemical techniques. The electron paramagnetic resonance characterization (EPR) showed well-resolved spectra in most solvents. In general the EPR spectra of [Cu(acac)2] show higher gz values and lower hyperfine coupling constants, A z, in ionic liquids than in organic solvents, in agreement with longer CuO bond lengths and higher electron charge in the copper ion in the ionic liquids, suggesting coordination of the ionic liquid anions. For [Cu(HFacac)2(H2O)] the opposite was observed suggesting that in ionic liquids there is no coordination of the anions and that the complex is tetrahedrically distorted. The redox properties of the Cu(II) complexes were investigated by cyclic voltammetry (CV) at a Pt electrode (d = 1 mm), in bmimBF4 and bmimNTf2 ionic liquids and, for comparative purposes, in neat organic solvents. The neutral copper(II) complexes undergo irreversible reductions to Cu(I) and Cu(0) species in both ILs and common organic solvents (CH2Cl2 or acetonitrile), but, in ILs, they are usually more easier to reduce (less cathodic reduction potential) than in the organic solvents. Moreover, 1 and 2 are easier to reduce in bmimNTf2 than in bmimBF4 ionic liquid.

AB - The behavior of copper(II) complexes of pentane-2,4-dione and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, [Cu(acac)2] (1) and [Cu(HFacac)2(H2O)] (2), in ionic liquids and molecular organic solvents, was studied by spectroscopic and electrochemical techniques. The electron paramagnetic resonance characterization (EPR) showed well-resolved spectra in most solvents. In general the EPR spectra of [Cu(acac)2] show higher gz values and lower hyperfine coupling constants, A z, in ionic liquids than in organic solvents, in agreement with longer CuO bond lengths and higher electron charge in the copper ion in the ionic liquids, suggesting coordination of the ionic liquid anions. For [Cu(HFacac)2(H2O)] the opposite was observed suggesting that in ionic liquids there is no coordination of the anions and that the complex is tetrahedrically distorted. The redox properties of the Cu(II) complexes were investigated by cyclic voltammetry (CV) at a Pt electrode (d = 1 mm), in bmimBF4 and bmimNTf2 ionic liquids and, for comparative purposes, in neat organic solvents. The neutral copper(II) complexes undergo irreversible reductions to Cu(I) and Cu(0) species in both ILs and common organic solvents (CH2Cl2 or acetonitrile), but, in ILs, they are usually more easier to reduce (less cathodic reduction potential) than in the organic solvents. Moreover, 1 and 2 are easier to reduce in bmimNTf2 than in bmimBF4 ionic liquid.

KW - Copper complexes

KW - EPR

KW - Ionic liquids

KW - Solvation

KW - Voltammetry

UR - http://www.scopus.com/inward/record.url?scp=84891865914&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84891865914&partnerID=8YFLogxK

U2 - 10.1016/j.molstruc.2013.12.025

DO - 10.1016/j.molstruc.2013.12.025

M3 - Article

VL - 1060

SP - 142

EP - 149

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

SN - 0022-2860

IS - 1

ER -