CaltechAUTHORS
  A Caltech Library Service

Immobilization and electrochemical properties of ruthenium and iridium complexes on carbon electrodes

Gupta, Ayush and Blakemore, James D. and Brunschwig, Bruce S. and Gray, Harry B. (2016) Immobilization and electrochemical properties of ruthenium and iridium complexes on carbon electrodes. Journal of Physics: Condensed Matter, 28 (9). Art. No. 094002. ISSN 0953-8984. doi:10.1088/0953-8984/28/9/094002. https://resolver.caltech.edu/CaltechAUTHORS:20160222-122103336

Full text is not posted in this repository. Consult Related URLs below.

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20160222-122103336

Abstract

We report the synthesis and surface immobilization of two new pyrene-appended molecular metal complexes: a ruthenium tris(bipyridyl) complex (1) and a bipyridyl complex of [Cp^*Ir] (2) (Cp^*  =  pentamethylcyclopentadienyl). X-ray photoelectron spectroscopy confirmed successful immobilization on high surface area carbon electrodes, with the expected elemental ratios for the desired compounds. Electrochemical data collected in acetonitrile solution revealed a reversible reduction of 1 near  −1.4 V, and reduction of 2 near  −0.75 V. The noncovalent immobilization, driven by association of the appended pyrene groups with the surface, was sufficiently stable to enable studies of the molecular electrochemistry. Electroactive surface coverage of 1 was diminished by only 27% over three hours soaking in electrolyte solution as measured by cyclic voltammetry. The electrochemical response of 2 resembled its soluble analogues, and suggested that ligand exchange occurred on the surface. Together, the results demonstrate that noncovalent immobilization routes are suitable for obtaining fundamental understanding of immobilized metal complexes and their reductive electrochemical properties.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1088/0953-8984/28/9/094002DOIArticle
ORCID:
AuthorORCID
Blakemore, James D.0000-0003-4172-7460
Brunschwig, Bruce S.0000-0002-6135-6727
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2016 IOP Publishing Ltd. Received 10 June 2015, revised 30 July 2015. Accepted for publication 11 August 2015. Published 12 February 2016. This research was carried out in part at the Molecular materials Research Center of the Beckman Institute at Caltech. The research was supported by the Resnick Sustainability Institute at Caltech (Postdoctoral Fellowship to J D B) and the NSF CCI Solar Fuels Program (CHE-1305124 and a CCI Postdoctoral Fellowship to J D B). The x-ray photoelectron spectroscopy was supported by a contract with the California Energy Commission (500-11-023).
Group:Resnick Sustainability Institute, CCI Solar Fuels
Funders:
Funding AgencyGrant Number
Caltech Beckman InstituteUNSPECIFIED
Resnick Sustainability InstituteUNSPECIFIED
NSFCHE-1305124
California Energy Commission500-11-023
Subject Keywords:surface chemistry, x-ray photoelectron spectroscopy, cyclic voltammetry, solar fuels
Issue or Number:9
DOI:10.1088/0953-8984/28/9/094002
Record Number:CaltechAUTHORS:20160222-122103336
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160222-122103336
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:64635
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:22 Feb 2016 20:55
Last Modified:12 Jul 2022 16:40

Repository Staff Only: item control page