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 language | English (US) |
|---|---|
| Pages (from-to) | 2810-2826 |
| Number of pages | 17 |
| Journal | Journal of Coordination Chemistry |
| Volume | 68 |
| Issue number | 16 |
| DOIs | |
| State | Published - Aug 18 2015 |
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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 journal › Article
}
TY - JOUR
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.
KW - Coordination chemistry
KW - Copper
KW - Crystallography
KW - Electrochemistry
KW - EPR
KW - Macrocycle
KW - Pyridine
UR - http://www.scopus.com/inward/record.url?scp=84939266374&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84939266374&partnerID=8YFLogxK
U2 - 10.1080/00958972.2015.1068935
DO - 10.1080/00958972.2015.1068935
M3 - Article
AN - SCOPUS:84939266374
VL - 68
SP - 2810
EP - 2826
JO - Journal of Coordination Chemistry
JF - Journal of Coordination Chemistry
SN - 0095-8972
IS - 16
ER -