Proton-coupled electron transfer and lewis acid recognition at self-assembled monolayers of an oxo-bridged diruthenium(III) complex functionalized with two disulfide anchors

Hua Xin Zhang; Masaaki Abe; Yi Zhang; Guofang Li; Shen Ye; Masatoshi Osawa; Yoichi Sasaki

doi:10.1021/la401736f

Proton-coupled electron transfer and lewis acid recognition at self-assembled monolayers of an oxo-bridged diruthenium(III) complex functionalized with two disulfide anchors

Hua Xin Zhang, Masaaki Abe, Yi Zhang, Guofang Li, Shen Ye, Masatoshi Osawa, Yoichi Sasaki

SCI - Chemistry

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

12 Citations (Scopus)

Abstract

A new μ-oxo-bis(μ-acetato)diruthenium(III) complex bearing two pyridyl disulfide ligands {[Ru₂(μ-O)(μ-OAc)₂(bpy) ₂(L_py-SS)₂](PF₆)₂ (OAc = CH₃CO₂^-, bpy = 2,2′-bipyridine, L _py-SS = (C₅H₄N)CH₂NHC(O)(CH ₂)₄CH(CH₂)₂SS) (1)} has been synthesized to prepare self-assembled monolayers (SAMs) on the Au(111) electrode surface. The SAMs have been characterized by contact-angle measurements, reflection-absorption surface infrared spectroscopy, cyclic voltammetry, and reductive desorption experiments. The SAMs exhibited proton-coupled electron transfer (PCET) reactions when the electrochemistry was studied in aqueous electrolyte solution (0.1 M NaClO₄ with Britton-Robinson buffer to adjust the solution pH). The potential-pH plot (Pourbaix diagram) in the pH range from 1 to 12 has established that the dinuclear ruthenium moiety was involved in the interfacial PCET processes with four distinct redox states: Ru^IIIRu^III(μ-O), Ru^IIRu^III(μ- OH), Ru^IIRu^II(μ-OH), and Ru^IIRu ^II(μ-OH₂). We also demonstrated that the interfacial redox processes were modulated by the addition of Lewis acids such as BF ₃ or Al³⁺ to the electrolyte media, in which the externally added Lewis acids interacted with μ-O of the dinuclear moiety within the SAMs.

Original language	English
Pages (from-to)	10110-10119
Number of pages	10
Journal	Langmuir
Volume	29
Issue number	32
DOIs	https://doi.org/10.1021/la401736f
Publication status	Published - 2013 Aug 13

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@article{56c745d764b14653a98a34ea324cbadf,

title = "Proton-coupled electron transfer and lewis acid recognition at self-assembled monolayers of an oxo-bridged diruthenium(III) complex functionalized with two disulfide anchors",

abstract = "A new μ-oxo-bis(μ-acetato)diruthenium(III) complex bearing two pyridyl disulfide ligands {[Ru2(μ-O)(μ-OAc)2(bpy) 2(Lpy-SS)2](PF6)2 (OAc = CH3CO2-, bpy = 2,2′-bipyridine, L py-SS = (C5H4N)CH2NHC(O)(CH 2)4CH(CH2)2SS) (1)} has been synthesized to prepare self-assembled monolayers (SAMs) on the Au(111) electrode surface. The SAMs have been characterized by contact-angle measurements, reflection-absorption surface infrared spectroscopy, cyclic voltammetry, and reductive desorption experiments. The SAMs exhibited proton-coupled electron transfer (PCET) reactions when the electrochemistry was studied in aqueous electrolyte solution (0.1 M NaClO4 with Britton-Robinson buffer to adjust the solution pH). The potential-pH plot (Pourbaix diagram) in the pH range from 1 to 12 has established that the dinuclear ruthenium moiety was involved in the interfacial PCET processes with four distinct redox states: RuIIIRuIII(μ-O), RuIIRuIII(μ- OH), RuIIRuII(μ-OH), and RuIIRu II(μ-OH2). We also demonstrated that the interfacial redox processes were modulated by the addition of Lewis acids such as BF 3 or Al3+ to the electrolyte media, in which the externally added Lewis acids interacted with μ-O of the dinuclear moiety within the SAMs.",

author = "Zhang, {Hua Xin} and Masaaki Abe and Yi Zhang and Guofang Li and Shen Ye and Masatoshi Osawa and Yoichi Sasaki",

year = "2013",

month = aug,

day = "13",

doi = "10.1021/la401736f",

language = "English",

volume = "29",

pages = "10110--10119",

journal = "Langmuir",

issn = "0743-7463",

publisher = "American Chemical Society",

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T1 - Proton-coupled electron transfer and lewis acid recognition at self-assembled monolayers of an oxo-bridged diruthenium(III) complex functionalized with two disulfide anchors

AU - Zhang, Hua Xin

AU - Abe, Masaaki

AU - Zhang, Yi

AU - Li, Guofang

AU - Ye, Shen

AU - Osawa, Masatoshi

AU - Sasaki, Yoichi

PY - 2013/8/13

Y1 - 2013/8/13

N2 - A new μ-oxo-bis(μ-acetato)diruthenium(III) complex bearing two pyridyl disulfide ligands {[Ru2(μ-O)(μ-OAc)2(bpy) 2(Lpy-SS)2](PF6)2 (OAc = CH3CO2-, bpy = 2,2′-bipyridine, L py-SS = (C5H4N)CH2NHC(O)(CH 2)4CH(CH2)2SS) (1)} has been synthesized to prepare self-assembled monolayers (SAMs) on the Au(111) electrode surface. The SAMs have been characterized by contact-angle measurements, reflection-absorption surface infrared spectroscopy, cyclic voltammetry, and reductive desorption experiments. The SAMs exhibited proton-coupled electron transfer (PCET) reactions when the electrochemistry was studied in aqueous electrolyte solution (0.1 M NaClO4 with Britton-Robinson buffer to adjust the solution pH). The potential-pH plot (Pourbaix diagram) in the pH range from 1 to 12 has established that the dinuclear ruthenium moiety was involved in the interfacial PCET processes with four distinct redox states: RuIIIRuIII(μ-O), RuIIRuIII(μ- OH), RuIIRuII(μ-OH), and RuIIRu II(μ-OH2). We also demonstrated that the interfacial redox processes were modulated by the addition of Lewis acids such as BF 3 or Al3+ to the electrolyte media, in which the externally added Lewis acids interacted with μ-O of the dinuclear moiety within the SAMs.

AB - A new μ-oxo-bis(μ-acetato)diruthenium(III) complex bearing two pyridyl disulfide ligands {[Ru2(μ-O)(μ-OAc)2(bpy) 2(Lpy-SS)2](PF6)2 (OAc = CH3CO2-, bpy = 2,2′-bipyridine, L py-SS = (C5H4N)CH2NHC(O)(CH 2)4CH(CH2)2SS) (1)} has been synthesized to prepare self-assembled monolayers (SAMs) on the Au(111) electrode surface. The SAMs have been characterized by contact-angle measurements, reflection-absorption surface infrared spectroscopy, cyclic voltammetry, and reductive desorption experiments. The SAMs exhibited proton-coupled electron transfer (PCET) reactions when the electrochemistry was studied in aqueous electrolyte solution (0.1 M NaClO4 with Britton-Robinson buffer to adjust the solution pH). The potential-pH plot (Pourbaix diagram) in the pH range from 1 to 12 has established that the dinuclear ruthenium moiety was involved in the interfacial PCET processes with four distinct redox states: RuIIIRuIII(μ-O), RuIIRuIII(μ- OH), RuIIRuII(μ-OH), and RuIIRu II(μ-OH2). We also demonstrated that the interfacial redox processes were modulated by the addition of Lewis acids such as BF 3 or Al3+ to the electrolyte media, in which the externally added Lewis acids interacted with μ-O of the dinuclear moiety within the SAMs.

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U2 - 10.1021/la401736f

DO - 10.1021/la401736f

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JO - Langmuir

JF - Langmuir

IS - 32

ER -

Proton-coupled electron transfer and lewis acid recognition at self-assembled monolayers of an oxo-bridged diruthenium(III) complex functionalized with two disulfide anchors

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