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

Research output: Contribution to journalArticlepeer-review

11 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(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.

Original languageEnglish
Pages (from-to)10110-10119
Number of pages10
JournalLangmuir
Volume29
Issue number32
DOIs
Publication statusPublished - 2013 Aug 13
Externally publishedYes

ASJC Scopus subject areas

  • Materials Science(all)
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Spectroscopy
  • Electrochemistry

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