TY - JOUR
T1 - Electrochemistry of homoleptic bis[3(4),12(13),21(22),30 (31)-tetra(teit-butyl)-naphthalocyaninato] rare earth(III) complexes
AU - Li, Renjie
AU - Zhang, Xianxi
AU - Pan, Na
AU - Zhu, Peihua
AU - Kobayashi, Nagao
AU - Jiang, Jianzhuang
PY - 2005
Y1 - 2005
N2 - The electrochemistry of homoleptic bis(naphthalocyaninato) double-decker complexes for the whole series of tervalent rare earths M(TBNc)2 (M = Y, La...Lu except Ce and Pm; H2TBNc = 3(4),12(13),21(22),30(31)-tetra(tert-butyl)naphthalocyanine) has been systematically studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Up to three quasi-reversible one-electron oxidations and four quasi-reversible one-electron reductions have been revealed for these double-deckers.The half-wave potentials of all oxidations and the first reduction for double-decker complexes are dependent on the size of the metal center. The difference between the redox potentials of the first and second reductions for MIII(TBNc)2, which represents the potential difference between the first oxidation and first reduction of [M III(TBNc)2]-, lies in the range 1.09-0.95 V and gradually diminishes along with the lanthanide contraction, indicating increased π-π interaction in the double-deckers in the same order. Comparison of electrochemical characteristics between M(TBNc)2 and M(TBPc)2 (H2TBPc = 2(3),9(10),16(17),24(25)-tetra(tert-butyl)-phthalocyanine) reveals that extension of the ligand conjugated system upon going from phthalocyanine to naphthalocyanine attenuates the ring-to-ring separation effect on the redox potentials of the double-deckers of the whole series of tervalent lanthanides.
AB - The electrochemistry of homoleptic bis(naphthalocyaninato) double-decker complexes for the whole series of tervalent rare earths M(TBNc)2 (M = Y, La...Lu except Ce and Pm; H2TBNc = 3(4),12(13),21(22),30(31)-tetra(tert-butyl)naphthalocyanine) has been systematically studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Up to three quasi-reversible one-electron oxidations and four quasi-reversible one-electron reductions have been revealed for these double-deckers.The half-wave potentials of all oxidations and the first reduction for double-decker complexes are dependent on the size of the metal center. The difference between the redox potentials of the first and second reductions for MIII(TBNc)2, which represents the potential difference between the first oxidation and first reduction of [M III(TBNc)2]-, lies in the range 1.09-0.95 V and gradually diminishes along with the lanthanide contraction, indicating increased π-π interaction in the double-deckers in the same order. Comparison of electrochemical characteristics between M(TBNc)2 and M(TBPc)2 (H2TBPc = 2(3),9(10),16(17),24(25)-tetra(tert-butyl)-phthalocyanine) reveals that extension of the ligand conjugated system upon going from phthalocyanine to naphthalocyanine attenuates the ring-to-ring separation effect on the redox potentials of the double-deckers of the whole series of tervalent lanthanides.
KW - Electrochemistry
KW - Naphthalocyanines
KW - Rare earths
KW - Sandwich complexes
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U2 - 10.1142/s1088424605000083
DO - 10.1142/s1088424605000083
M3 - Article
AN - SCOPUS:20844432762
SN - 1088-4246
VL - 9
SP - 40
EP - 46
JO - Journal of Porphyrins and Phthalocyanines
JF - Journal of Porphyrins and Phthalocyanines
IS - 1
ER -