Issue 10, 2014

NIR electrochemiluminescence from Au25 nanoclusters facilitated by highly oxidizing and reducing co-reactant radicals

Abstract

The well-defined electrochemical features and optical properties of the negatively charged Au25 clusters (Au25) provide opportunities for a photoelectrochemical study by means of electrochemiluminescence (ECL) technique. Under annihilation conditions where the Au25 is electrochemically pumped to its various oxidized and reduced forms showed no appreciable ECL light emission, due presumably to the short lifetime of the electrogenerated intermediates and their reactivity. Interestingly, in either Au25/tri-n-propylamine (TPrA) or Au25/benzoyl peroxide (BPO) co-reactant systems, the correspondingly highly reducing and oxidizing intermediates electrogenerated from TPrA and BPO lead to light emission at 950 and 890 nm in near-infrared (NIR) region. The ECL in the presence of various concentrations of TPrA (6.3, 12.5, 25, 50, 100 and 200 mM) and BPO (2.5, 5, 25 and 50 mM) was explicitly investigated. Along with the concentration dependence study, spooling ECL spectroscopy provided insight into the ECL mechanisms. Notably, while the Au25* is the main light emission source with BPO, ECL in the presence of TPrA is attributed to emissions from the Au25*, Au250* and Au25+* that are tuneable by means of the applied potential and TPrA concentration.

Graphical abstract: NIR electrochemiluminescence from Au25− nanoclusters facilitated by highly oxidizing and reducing co-reactant radicals

Supplementary files

Article information

Article type
Edge Article
Submitted
14 Apr 2014
Accepted
04 Jun 2014
First published
16 Jun 2014

Chem. Sci., 2014,5, 3814-3822

Author version available

NIR electrochemiluminescence from Au25 nanoclusters facilitated by highly oxidizing and reducing co-reactant radicals

M. Hesari, M. S. Workentin and Z. Ding, Chem. Sci., 2014, 5, 3814 DOI: 10.1039/C4SC01086H

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