Tuning of the [Cu3(μ-O)]4+/5+ redox couple: Spectroscopic evidence of charge delocalization in the mixed-valent [Cu 3(μ-O)]5+ species

Marlyn Rivera-Carrillo; Indranil Chakraborty; Gellert Mezei; Richard D. Webster; Raphael G. Raptis

doi:10.1021/ic800531y

Tuning of the [Cu₃(μ-O)]^4+/5+ redox couple: Spectroscopic evidence of charge delocalization in the mixed-valent [Cu ₃(μ-O)]⁵⁺ species

Marlyn Rivera-Carrillo, Indranil Chakraborty, Gellert Mezei, Richard D. Webster, Raphael G. Raptis

Research output: Contribution to journal › Article › peer-review

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Abstract

Trinuclear Cu^II-complexes of formula [Cu^II ₃(μ₃-E)(μ-4-R-pz)₃X₃] ^±n, E = O and OH; R = H, Cl, Br, CH(O) and NO₂; X = Cl, NCS, CH₃COO, and py, have been synthesized and characterized and the effect of substitution of terminal ligands, as well as 4-R-groups, in the one-electron oxidation process has been investigated by cyclic voltammetry. In situ UV-vis-NIR spectroelectrochemical characterization of the mixed valence Cu₃⁷⁺-complex [Cu₃(μ₃-O)(μ-pz) ₃Cl₃]^- revealed an intervalence charge transfer band at 9550 cm^-1 (ε = 2600 cm^-1 M^-1), whose analysis identifies this species as a delocalized, Robin-Day class-III system, with an electronic coupling factor, H_ab, of 4775 cm ^-1.

Original language	English
Pages (from-to)	7644-7650
Number of pages	7
Journal	Inorganic Chemistry
Volume	47
Issue number	17
DOIs	https://doi.org/10.1021/ic800531y
Publication status	Published - Sept 1 2008
Externally published	Yes

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Tuning of the [Cu3(μ-O)]4+/5+ redox couple: Spectroscopic evidence of charge delocalization in the mixed-valent [Cu 3(μ-O)]5+ species",

abstract = "Trinuclear CuII-complexes of formula [CuII 3(μ3-E)(μ-4-R-pz)3X3] ±n, E = O and OH; R = H, Cl, Br, CH(O) and NO2; X = Cl, NCS, CH3COO, and py, have been synthesized and characterized and the effect of substitution of terminal ligands, as well as 4-R-groups, in the one-electron oxidation process has been investigated by cyclic voltammetry. In situ UV-vis-NIR spectroelectrochemical characterization of the mixed valence Cu37+-complex [Cu3(μ3-O)(μ-pz) 3Cl3]- revealed an intervalence charge transfer band at 9550 cm-1 (ε = 2600 cm-1 M-1), whose analysis identifies this species as a delocalized, Robin-Day class-III system, with an electronic coupling factor, Hab, of 4775 cm -1.",

author = "Marlyn Rivera-Carrillo and Indranil Chakraborty and Gellert Mezei and Webster, \{Richard D.\} and Raptis, \{Raphael G.\}",

year = "2008",

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doi = "10.1021/ic800531y",

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T1 - Tuning of the [Cu3(μ-O)]4+/5+ redox couple

T2 - Spectroscopic evidence of charge delocalization in the mixed-valent [Cu 3(μ-O)]5+ species

AU - Rivera-Carrillo, Marlyn

AU - Chakraborty, Indranil

AU - Mezei, Gellert

AU - Webster, Richard D.

AU - Raptis, Raphael G.

PY - 2008/9/1

Y1 - 2008/9/1

N2 - Trinuclear CuII-complexes of formula [CuII 3(μ3-E)(μ-4-R-pz)3X3] ±n, E = O and OH; R = H, Cl, Br, CH(O) and NO2; X = Cl, NCS, CH3COO, and py, have been synthesized and characterized and the effect of substitution of terminal ligands, as well as 4-R-groups, in the one-electron oxidation process has been investigated by cyclic voltammetry. In situ UV-vis-NIR spectroelectrochemical characterization of the mixed valence Cu37+-complex [Cu3(μ3-O)(μ-pz) 3Cl3]- revealed an intervalence charge transfer band at 9550 cm-1 (ε = 2600 cm-1 M-1), whose analysis identifies this species as a delocalized, Robin-Day class-III system, with an electronic coupling factor, Hab, of 4775 cm -1.

AB - Trinuclear CuII-complexes of formula [CuII 3(μ3-E)(μ-4-R-pz)3X3] ±n, E = O and OH; R = H, Cl, Br, CH(O) and NO2; X = Cl, NCS, CH3COO, and py, have been synthesized and characterized and the effect of substitution of terminal ligands, as well as 4-R-groups, in the one-electron oxidation process has been investigated by cyclic voltammetry. In situ UV-vis-NIR spectroelectrochemical characterization of the mixed valence Cu37+-complex [Cu3(μ3-O)(μ-pz) 3Cl3]- revealed an intervalence charge transfer band at 9550 cm-1 (ε = 2600 cm-1 M-1), whose analysis identifies this species as a delocalized, Robin-Day class-III system, with an electronic coupling factor, Hab, of 4775 cm -1.

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Tuning of the [Cu₃(μ-O)]^4+/5+ redox couple: Spectroscopic evidence of charge delocalization in the mixed-valent [Cu ₃(μ-O)]⁵⁺ species

Abstract

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