Chemical characteristics of the products of the complexation reaction between copper(II) and a tetra-aza macrocycle in the presence of chloride ions

Kimberly M. Lincoln, Netzahualcoyotl Arroyo-Curras, Hannah M. Johnston, Travis D. Hayden, Brad S. Pierce, Nattamai Bhuvanesh, Kayla N. Green

Research output: Contribution to journalArticle

Abstract

(Figure Presented). The reaction of copper(II) perchlorate with the hydrochloride salt of 3,6,9,15-tetra-azabicyclo[9.3.1]penta-deca-1,11,13-triene (L1) in acetonitrile forms two macrocyclic complexes that can be characterized: [L1CuIICl][ClO4] (1) and [L1CuIICl]2[CuCl4] (2). The structural, electronic, and redox properties of these complexes were studied using spectroscopy (EPR and UV-visible) and electrochemistry. In addition, the solid-state structure of 1 was obtained using X-ray diffraction. The copper(II) is five-coordinate ligated by four N-atoms of the macrocycle and a chloride atom. EPR studies of 1 both in DMF and aqueous solution indicate the presence of a single copper(II) species. In contrast, EPR studies of 2 performed in frozen DMF and in the solid-state reveal the presence of two spectroscopically distinct copper(II) complexes assigned as [L1CuIICl]+ and [CuIICl4]2-. Lastly, electrochemical studies demonstrate that both [L1CuIICl]+ and [CuIICl4]2- are redox active. Specifically, the [L1CuIICl]+ undergoes a quasi-reversible Cu(II)/(I) redox reaction in the absence of excess chloride. In the presence of chloride, however, the chemical irreversibility of this couple becomes evident at concentrations of chloride that exceed 50 mM. As a result, the presence of chloride from the chemical equilibrium of this latter species impedes the reversibility of the reduction of [L1CuIICl]+ to [L1CuICl]0.

Original languageEnglish (US)
Pages (from-to)2810-2826
Number of pages17
JournalJournal of Coordination Chemistry
Volume68
Issue number16
DOIs
StatePublished - Aug 18 2015

Fingerprint

Complexation
Chlorides
Copper
chlorides
Ions
Paramagnetic resonance
copper
products
ions
Atoms
Redox reactions
trienes
solid state
Electrochemistry
Acetonitrile
hydrochlorides
electrochemistry
perchlorates
acetonitrile
Spectroscopy

Keywords

  • Coordination chemistry
  • Copper
  • Crystallography
  • Electrochemistry
  • EPR
  • Macrocycle
  • Pyridine

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Chemical characteristics of the products of the complexation reaction between copper(II) and a tetra-aza macrocycle in the presence of chloride ions. / Lincoln, Kimberly M.; Arroyo-Curras, Netzahualcoyotl; Johnston, Hannah M.; Hayden, Travis D.; Pierce, Brad S.; Bhuvanesh, Nattamai; Green, Kayla N.

In: Journal of Coordination Chemistry, Vol. 68, No. 16, 18.08.2015, p. 2810-2826.

Research output: Contribution to journalArticle

Lincoln, Kimberly M. ; Arroyo-Curras, Netzahualcoyotl ; Johnston, Hannah M. ; Hayden, Travis D. ; Pierce, Brad S. ; Bhuvanesh, Nattamai ; Green, Kayla N. / Chemical characteristics of the products of the complexation reaction between copper(II) and a tetra-aza macrocycle in the presence of chloride ions. In: Journal of Coordination Chemistry. 2015 ; Vol. 68, No. 16. pp. 2810-2826.
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abstract = "(Figure Presented). The reaction of copper(II) perchlorate with the hydrochloride salt of 3,6,9,15-tetra-azabicyclo[9.3.1]penta-deca-1,11,13-triene (L1) in acetonitrile forms two macrocyclic complexes that can be characterized: [L1CuIICl][ClO4] (1) and [L1CuIICl]2[CuCl4] (2). The structural, electronic, and redox properties of these complexes were studied using spectroscopy (EPR and UV-visible) and electrochemistry. In addition, the solid-state structure of 1 was obtained using X-ray diffraction. The copper(II) is five-coordinate ligated by four N-atoms of the macrocycle and a chloride atom. EPR studies of 1 both in DMF and aqueous solution indicate the presence of a single copper(II) species. In contrast, EPR studies of 2 performed in frozen DMF and in the solid-state reveal the presence of two spectroscopically distinct copper(II) complexes assigned as [L1CuIICl]+ and [CuIICl4]2-. Lastly, electrochemical studies demonstrate that both [L1CuIICl]+ and [CuIICl4]2- are redox active. Specifically, the [L1CuIICl]+ undergoes a quasi-reversible Cu(II)/(I) redox reaction in the absence of excess chloride. In the presence of chloride, however, the chemical irreversibility of this couple becomes evident at concentrations of chloride that exceed 50 mM. As a result, the presence of chloride from the chemical equilibrium of this latter species impedes the reversibility of the reduction of [L1CuIICl]+ to [L1CuICl]0.",
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T1 - Chemical characteristics of the products of the complexation reaction between copper(II) and a tetra-aza macrocycle in the presence of chloride ions

AU - Lincoln, Kimberly M.

AU - Arroyo-Curras, Netzahualcoyotl

AU - Johnston, Hannah M.

AU - Hayden, Travis D.

AU - Pierce, Brad S.

AU - Bhuvanesh, Nattamai

AU - Green, Kayla N.

PY - 2015/8/18

Y1 - 2015/8/18

N2 - (Figure Presented). The reaction of copper(II) perchlorate with the hydrochloride salt of 3,6,9,15-tetra-azabicyclo[9.3.1]penta-deca-1,11,13-triene (L1) in acetonitrile forms two macrocyclic complexes that can be characterized: [L1CuIICl][ClO4] (1) and [L1CuIICl]2[CuCl4] (2). The structural, electronic, and redox properties of these complexes were studied using spectroscopy (EPR and UV-visible) and electrochemistry. In addition, the solid-state structure of 1 was obtained using X-ray diffraction. The copper(II) is five-coordinate ligated by four N-atoms of the macrocycle and a chloride atom. EPR studies of 1 both in DMF and aqueous solution indicate the presence of a single copper(II) species. In contrast, EPR studies of 2 performed in frozen DMF and in the solid-state reveal the presence of two spectroscopically distinct copper(II) complexes assigned as [L1CuIICl]+ and [CuIICl4]2-. Lastly, electrochemical studies demonstrate that both [L1CuIICl]+ and [CuIICl4]2- are redox active. Specifically, the [L1CuIICl]+ undergoes a quasi-reversible Cu(II)/(I) redox reaction in the absence of excess chloride. In the presence of chloride, however, the chemical irreversibility of this couple becomes evident at concentrations of chloride that exceed 50 mM. As a result, the presence of chloride from the chemical equilibrium of this latter species impedes the reversibility of the reduction of [L1CuIICl]+ to [L1CuICl]0.

AB - (Figure Presented). The reaction of copper(II) perchlorate with the hydrochloride salt of 3,6,9,15-tetra-azabicyclo[9.3.1]penta-deca-1,11,13-triene (L1) in acetonitrile forms two macrocyclic complexes that can be characterized: [L1CuIICl][ClO4] (1) and [L1CuIICl]2[CuCl4] (2). The structural, electronic, and redox properties of these complexes were studied using spectroscopy (EPR and UV-visible) and electrochemistry. In addition, the solid-state structure of 1 was obtained using X-ray diffraction. The copper(II) is five-coordinate ligated by four N-atoms of the macrocycle and a chloride atom. EPR studies of 1 both in DMF and aqueous solution indicate the presence of a single copper(II) species. In contrast, EPR studies of 2 performed in frozen DMF and in the solid-state reveal the presence of two spectroscopically distinct copper(II) complexes assigned as [L1CuIICl]+ and [CuIICl4]2-. Lastly, electrochemical studies demonstrate that both [L1CuIICl]+ and [CuIICl4]2- are redox active. Specifically, the [L1CuIICl]+ undergoes a quasi-reversible Cu(II)/(I) redox reaction in the absence of excess chloride. In the presence of chloride, however, the chemical irreversibility of this couple becomes evident at concentrations of chloride that exceed 50 mM. As a result, the presence of chloride from the chemical equilibrium of this latter species impedes the reversibility of the reduction of [L1CuIICl]+ to [L1CuICl]0.

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KW - Copper

KW - Crystallography

KW - Electrochemistry

KW - EPR

KW - Macrocycle

KW - Pyridine

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