Multicopper models for the laccase active site: Effect of nuclearity on electrocatalytic oxygen reduction

Edmund C.M. Tse, David Schilter, Danielle L. Gray, Thomas B. Rauchfuss, Andrew A. Gewirth

Research output: Contribution to journalArticlepeer-review

Abstract

Cu complexes of 2,2'-dipicolylamine (DPA) were prepared and tested as electrocatalysts for the oxygen reduction reaction (ORR). To study the effect of multinuclearity on the ORR, two Cu-DPA units were connected with a flexible linker, and a third metal-binding pocket was installed in the ligand framework. ORR onset potentials and the diffusion-limited current densities of di- and tricopper complexes of DPA derivatives were found to be comparable to those of the simpler Cu-DPA system. Electrochemical analyses, crystallographic data, and metal-substitution studies suggested that Cu complexes of DPA derivatives reacted with O2 via a binuclear intermolecular pathway but that the Cu center in the third binding site did not participate in the ORR process. This study highlights the viability of Cu-DPA complexes to mimic the T3-site of laccase, and serves as a guide for designing future laccase models.

Original languageEnglish (US)
Pages (from-to)8505-8516
Number of pages12
JournalInorganic Chemistry
Volume53
Issue number16
DOIs
StatePublished - Aug 18 2014

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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