New copper(ii)-centered complexes with organometallic donor-acceptor substituted unsymmetrical Schiff base ligands

Alexander Trujillo, Frédéric Justaud, Loïc Toupet, Olivier Cador, David Carrillo, Carolina Manzur, Jean René Hamon

Resultado de la investigación: Article

20 Citas (Scopus)

Resumen

The synthesis and full characterization using various spectroscopic techniques and single-crystal X-ray diffraction analysis of a family of three robust copper(ii)-centered complexes with organometallic donor-acceptor substituted unsymmetrical Schiff base ligands, namely, the binuclear derivatives Cu[Fc-C(O)CHC(CH3)N-X-NCH-(2-O,5-Br-C6H3)] (3: X = o-C6H4, 4: X = CH2CH2), and the corresponding ionic trinuclear counterpart of 4, [Cu{Fc-C(O)CHC(CH 3)N-CH2CH2-NCH-(η6-2-O,5-Br- C6H3)RuCp*}][PF6] (5) (Fc = (η5-C5H5)Fe(η5-C 5H4), Cp* = η5-C5Me 5), have been explored. Single crystal X-ray diffraction analysis of complex 3 indicates a bowed structure of the unsymmetrical Schiff base scaffold. The Cu2+ ion is tetracoordinated in a square planar environment, with two nitrogen atoms and two oxygen atoms as donors. The EPR spectra of solid trinuclear complexes 5 and 7 (unsubstituted salicylidene ring and X = o-C 6H4) at low temperature (68 K) consisted of fine-structure transitions (ΔMs = ±1) with zero-field splitting (ZFS) values of 0.0458 and 0.0415 cm-1, respectively, and a half-field signal (ΔMs = ±2) at ca. 1600 G, suggesting the formation of dimeric species (S = 1). In those dimers, Cu-Cu distances of 3.97 and 4.14 Å, respectively, are computed from ZFS terms. The variable-temperature (2-300 K) magnetic susceptibilities of powdered samples of 5 and 7 have been measured, and an intermolecular antiferromagnetic interaction with exchange couplings of J = -1.05 and -0.65 cm-1, respectively, were found. The electrochemical behavior of both the neutral binuclear and ionic trinuclear compounds was investigated by cyclic voltammetry. Notably, the ability of the copper Schiff base core to transmit electronic effects between the two organometallic termini has been demonstrated by the observed anodic shift of the reversible voltammetric signal ascribed to the FeII/FeIII couple of the ferrocenyl donor fragment.

Idioma originalEnglish
Páginas (desde-hasta)2027-2036
Número de páginas10
PublicaciónNew Journal of Chemistry
Volumen35
N.º10
DOI
EstadoPublished - 1 oct 2011

Huella dactilar

Schiff Bases
Organometallics
X ray diffraction analysis
Copper
Ligands
Single crystals
Atoms
Exchange coupling
Magnetic susceptibility
Scaffolds
Dimers
Cyclic voltammetry
Paramagnetic resonance
Nitrogen
Derivatives
Temperature
Oxygen
Ions

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Materials Chemistry

Citar esto

Trujillo, Alexander ; Justaud, Frédéric ; Toupet, Loïc ; Cador, Olivier ; Carrillo, David ; Manzur, Carolina ; Hamon, Jean René. / New copper(ii)-centered complexes with organometallic donor-acceptor substituted unsymmetrical Schiff base ligands. En: New Journal of Chemistry. 2011 ; Vol. 35, N.º 10. pp. 2027-2036.
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title = "New copper(ii)-centered complexes with organometallic donor-acceptor substituted unsymmetrical Schiff base ligands",
abstract = "The synthesis and full characterization using various spectroscopic techniques and single-crystal X-ray diffraction analysis of a family of three robust copper(ii)-centered complexes with organometallic donor-acceptor substituted unsymmetrical Schiff base ligands, namely, the binuclear derivatives Cu[Fc-C(O)CHC(CH3)N-X-NCH-(2-O,5-Br-C6H3)] (3: X = o-C6H4, 4: X = CH2CH2), and the corresponding ionic trinuclear counterpart of 4, [Cu{Fc-C(O)CHC(CH 3)N-CH2CH2-NCH-(η6-2-O,5-Br- C6H3)RuCp*}][PF6] (5) (Fc = (η5-C5H5)Fe(η5-C 5H4), Cp* = η5-C5Me 5), have been explored. Single crystal X-ray diffraction analysis of complex 3 indicates a bowed structure of the unsymmetrical Schiff base scaffold. The Cu2+ ion is tetracoordinated in a square planar environment, with two nitrogen atoms and two oxygen atoms as donors. The EPR spectra of solid trinuclear complexes 5 and 7 (unsubstituted salicylidene ring and X = o-C 6H4) at low temperature (68 K) consisted of fine-structure transitions (ΔMs = ±1) with zero-field splitting (ZFS) values of 0.0458 and 0.0415 cm-1, respectively, and a half-field signal (ΔMs = ±2) at ca. 1600 G, suggesting the formation of dimeric species (S = 1). In those dimers, Cu-Cu distances of 3.97 and 4.14 {\AA}, respectively, are computed from ZFS terms. The variable-temperature (2-300 K) magnetic susceptibilities of powdered samples of 5 and 7 have been measured, and an intermolecular antiferromagnetic interaction with exchange couplings of J = -1.05 and -0.65 cm-1, respectively, were found. The electrochemical behavior of both the neutral binuclear and ionic trinuclear compounds was investigated by cyclic voltammetry. Notably, the ability of the copper Schiff base core to transmit electronic effects between the two organometallic termini has been demonstrated by the observed anodic shift of the reversible voltammetric signal ascribed to the FeII/FeIII couple of the ferrocenyl donor fragment.",
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New copper(ii)-centered complexes with organometallic donor-acceptor substituted unsymmetrical Schiff base ligands. / Trujillo, Alexander; Justaud, Frédéric; Toupet, Loïc; Cador, Olivier; Carrillo, David; Manzur, Carolina; Hamon, Jean René.

En: New Journal of Chemistry, Vol. 35, N.º 10, 01.10.2011, p. 2027-2036.

Resultado de la investigación: Article

TY - JOUR

T1 - New copper(ii)-centered complexes with organometallic donor-acceptor substituted unsymmetrical Schiff base ligands

AU - Trujillo, Alexander

AU - Justaud, Frédéric

AU - Toupet, Loïc

AU - Cador, Olivier

AU - Carrillo, David

AU - Manzur, Carolina

AU - Hamon, Jean René

PY - 2011/10/1

Y1 - 2011/10/1

N2 - The synthesis and full characterization using various spectroscopic techniques and single-crystal X-ray diffraction analysis of a family of three robust copper(ii)-centered complexes with organometallic donor-acceptor substituted unsymmetrical Schiff base ligands, namely, the binuclear derivatives Cu[Fc-C(O)CHC(CH3)N-X-NCH-(2-O,5-Br-C6H3)] (3: X = o-C6H4, 4: X = CH2CH2), and the corresponding ionic trinuclear counterpart of 4, [Cu{Fc-C(O)CHC(CH 3)N-CH2CH2-NCH-(η6-2-O,5-Br- C6H3)RuCp*}][PF6] (5) (Fc = (η5-C5H5)Fe(η5-C 5H4), Cp* = η5-C5Me 5), have been explored. Single crystal X-ray diffraction analysis of complex 3 indicates a bowed structure of the unsymmetrical Schiff base scaffold. The Cu2+ ion is tetracoordinated in a square planar environment, with two nitrogen atoms and two oxygen atoms as donors. The EPR spectra of solid trinuclear complexes 5 and 7 (unsubstituted salicylidene ring and X = o-C 6H4) at low temperature (68 K) consisted of fine-structure transitions (ΔMs = ±1) with zero-field splitting (ZFS) values of 0.0458 and 0.0415 cm-1, respectively, and a half-field signal (ΔMs = ±2) at ca. 1600 G, suggesting the formation of dimeric species (S = 1). In those dimers, Cu-Cu distances of 3.97 and 4.14 Å, respectively, are computed from ZFS terms. The variable-temperature (2-300 K) magnetic susceptibilities of powdered samples of 5 and 7 have been measured, and an intermolecular antiferromagnetic interaction with exchange couplings of J = -1.05 and -0.65 cm-1, respectively, were found. The electrochemical behavior of both the neutral binuclear and ionic trinuclear compounds was investigated by cyclic voltammetry. Notably, the ability of the copper Schiff base core to transmit electronic effects between the two organometallic termini has been demonstrated by the observed anodic shift of the reversible voltammetric signal ascribed to the FeII/FeIII couple of the ferrocenyl donor fragment.

AB - The synthesis and full characterization using various spectroscopic techniques and single-crystal X-ray diffraction analysis of a family of three robust copper(ii)-centered complexes with organometallic donor-acceptor substituted unsymmetrical Schiff base ligands, namely, the binuclear derivatives Cu[Fc-C(O)CHC(CH3)N-X-NCH-(2-O,5-Br-C6H3)] (3: X = o-C6H4, 4: X = CH2CH2), and the corresponding ionic trinuclear counterpart of 4, [Cu{Fc-C(O)CHC(CH 3)N-CH2CH2-NCH-(η6-2-O,5-Br- C6H3)RuCp*}][PF6] (5) (Fc = (η5-C5H5)Fe(η5-C 5H4), Cp* = η5-C5Me 5), have been explored. Single crystal X-ray diffraction analysis of complex 3 indicates a bowed structure of the unsymmetrical Schiff base scaffold. The Cu2+ ion is tetracoordinated in a square planar environment, with two nitrogen atoms and two oxygen atoms as donors. The EPR spectra of solid trinuclear complexes 5 and 7 (unsubstituted salicylidene ring and X = o-C 6H4) at low temperature (68 K) consisted of fine-structure transitions (ΔMs = ±1) with zero-field splitting (ZFS) values of 0.0458 and 0.0415 cm-1, respectively, and a half-field signal (ΔMs = ±2) at ca. 1600 G, suggesting the formation of dimeric species (S = 1). In those dimers, Cu-Cu distances of 3.97 and 4.14 Å, respectively, are computed from ZFS terms. The variable-temperature (2-300 K) magnetic susceptibilities of powdered samples of 5 and 7 have been measured, and an intermolecular antiferromagnetic interaction with exchange couplings of J = -1.05 and -0.65 cm-1, respectively, were found. The electrochemical behavior of both the neutral binuclear and ionic trinuclear compounds was investigated by cyclic voltammetry. Notably, the ability of the copper Schiff base core to transmit electronic effects between the two organometallic termini has been demonstrated by the observed anodic shift of the reversible voltammetric signal ascribed to the FeII/FeIII couple of the ferrocenyl donor fragment.

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U2 - 10.1039/c0nj01018a

DO - 10.1039/c0nj01018a

M3 - Article

AN - SCOPUS:80053360795

VL - 35

SP - 2027

EP - 2036

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 10

ER -