Cathodic electrochemiluminescence of acetonitrile, acetonitrile–1,10‐phenanthroline and acetonitrile–ternary Eu(III) complexes at a gold electrode

Abstract

Cathodic electrochemiluminescence (ECL) behaviours of the acetonitrile, acetonitrile-1,10-phenanthroline (phen) and acetonitrile-ternary Eu(III) complex systems at a gold electrode were studied. One very weak cathodic ECL-2 at -3.5 V was observed in 0.1 mol/L tetrabutylammonium tetrafluoroborate (TBABF(4)) acetonitrile solution. When 10 mmol/L tetrabutylammonium peroxydisulphate [(TBA)(2)S(2)O(8)] was added to 0.1 mol/L TBABF(4) acetonitrile solution, another cathodic ECL-1 at -2.7 V appeared and the potential for ECL-2 was shifted from -3.5 to -3.1 V. Furthermore, ECL-2 intensity was enhanced about 20-fold. When 1 x 10(-4) mol/L phen was added to 0.1 mol/L TBABF(4) + 10 mmol/L (TBA)(2)S(2)O(8) acetonitrile solution, the ECL intensities of ECL-1 and ECL-2 were enhanced about 20-fold compared with those of 0.1 mol/L TBABF(4) + 10 mmol/L (TBA)(2)S(2)O(8) acetonitrile solution. The maximum emission peaks of ECL-1 and ECL-2 in the three systems mentioned above appeared at about 530 nm. The products obtained by electrolysing 0.1 mol/L TBABF(4) acetonitrile solution at -3.5 V for 20 min were analysed by Fourier Transform Infrared (FTIR) spectra and gas chromatography-mass spectrometry (GC-MS) and the emitter of ECL-1 and ECL-2 was identified as excited state polyacetonitrile. When ternary Eu(III) complexes were presented in 0.1 mol/L TBABF(4) + 10 mmol/L (TBA)(2)S(2)O(8) acetonitrile solution, another maximum emission peak with a narrow band centred at about 610 nm appeared in ECL-1 in addition to the maximum emission peaks at about 530 nm for ECL-1 and ECL-2. The emitter of ECL emission at 610 nm was identified as the excited states Eu(III)*. The mechanisms for cathodic ECL behaviours of the acetonitrile, acetonitrile-phen and acetonitrile-ternary Eu(III) complex systems at a gold electrode have been proposed. The extremely sharp emission bands for ternary Eu(III) complexes may have analytical potential.

Electrogenerated Chemiluminescence and Electronic States of Several Organometallic Eu(III) and Tb(III) Complexes: Effects of the Ligands

“…al., reported ECL spectra of Eu(tta) 3 phen and Eu(dbm) 3 phen in the presence of S 2 O 8 2− using a Au electrode. They observed a sharp (λ ECL =∼ 610 nm) spectrum originated from the f‐f transition on top of a broad component (λ ECL =∼ 530 nm) derived from polymerized MeCN at a more negative potential than the limit of the negative end of the polarized potential window (−2.6 V vs Ag/AgCl) . Our results confirmed that the ECL based on the f‐f transitions of the Eu(III) complexes were able to be observed at a less negative potential, and coordinated ligands may cause broad emissions.…”

In Situ Synthesis of a Hierarchical All‐Solid‐State Electrolyte Based on Nitrile Materials for High‐Performance Lithium‐Ion Batteries

“…[ 15 ] With addition of PVA-CN to SN, a new peak at 1103 cm −1 appears, which belongs to the stretching vibration of C-O-C on PVA-CN ( Figure S3, Supporting Information), [ 21 ] while the peak appearing at 1059 cm −1 after LITFSI and LiPF 6 dissolved in SN is assigned to the stretching vibration of S-N-S on LITFSI (Figure 3 a). [ 22 ] As shown in Figure 3 b, an obvious new peak at 1557 cm −1 assigned to the stretching vibration of C-N appears in the FTIR spectrum of PVA-CN/SN solid electrolyte, [ 23 ] indicating a new conjugated structure with C-N bonds is formed and PVA-CN monomers are successfully polymerized in the SN-based solid electrolyte.…”

Investigation of cyano resin-based gel polymer electrolyte: in situ gelation mechanism and electrode–electrolyte interfacial fabrication in lithium-ion battery

“…25 The FTIR spectrum of the polymer matrix shows that the absorption peak at around 2250 cm À1 belonging to C^N bonds almost disappears, whereas the intensity of peak at 1670 cm À1 apparently increases, indicating the presence of C]N bonds in the polymer matrix. 26 The result of the FTIR spectrum demonstrates that the C^N bonds were cleaved in the gelation reaction of PVA-CN and a new conjugated structure with C]N bonds was formed.…”