TY - JOUR
T1 - Insights into electrochemiluminescent enhancement through electrode surface modification
AU - O'Reilly, Emmet J.
AU - Keyes, Tia E.
AU - Forster, Robert J.
AU - Dennany, Lynn
PY - 2013/1/21
Y1 - 2013/1/21
N2 - The electrochemiluminescent (ECL) properties of a luminescent metal centre, [Ru(bpy)3]2+, can be significantly modulated through its electronic interaction with neighbouring centres and the polymer backbone used to confine it on an electrode surface. From the perspective of ECL based sensing devices, an increase in the ECL efficiency of a metallopolymer film can result in enhanced sensor sensitivity and selectivity. This work probes the ECL properties of both conjugated, [Ru(bpy)2(PPyBBIM)10] 2+, and non-conjugated, [Ru(bpy)2(PVP)10] 2+, ruthenium based metallopolymer films based on a well documented reaction with sodium oxalate, where bpy is 2,2′-bipyridyl, PPYBBIM is poly[2-(2-pyridyl)-bibenzimidazole] and PVP is poly(4-vinylpyridine). Through a combination of ground state electrochemical studies and ECL measurements, the ECL efficiency for each film is determined. This study reveals that despite a dramatic influence in charge transfer rates between metal centres, as observed for the conducting polymer, mediated through the conducting polymer backbone, a corresponding increase in ECL efficiency is not always observed. The degree of communication between the adjacent excited state metal centres are an important consideration for ECL enhancement however self quenching, luminophore distribution and film porosity must also be considered.
AB - The electrochemiluminescent (ECL) properties of a luminescent metal centre, [Ru(bpy)3]2+, can be significantly modulated through its electronic interaction with neighbouring centres and the polymer backbone used to confine it on an electrode surface. From the perspective of ECL based sensing devices, an increase in the ECL efficiency of a metallopolymer film can result in enhanced sensor sensitivity and selectivity. This work probes the ECL properties of both conjugated, [Ru(bpy)2(PPyBBIM)10] 2+, and non-conjugated, [Ru(bpy)2(PVP)10] 2+, ruthenium based metallopolymer films based on a well documented reaction with sodium oxalate, where bpy is 2,2′-bipyridyl, PPYBBIM is poly[2-(2-pyridyl)-bibenzimidazole] and PVP is poly(4-vinylpyridine). Through a combination of ground state electrochemical studies and ECL measurements, the ECL efficiency for each film is determined. This study reveals that despite a dramatic influence in charge transfer rates between metal centres, as observed for the conducting polymer, mediated through the conducting polymer backbone, a corresponding increase in ECL efficiency is not always observed. The degree of communication between the adjacent excited state metal centres are an important consideration for ECL enhancement however self quenching, luminophore distribution and film porosity must also be considered.
UR - http://www.scopus.com/inward/record.url?scp=84870884339&partnerID=8YFLogxK
U2 - 10.1039/c2an36045d
DO - 10.1039/c2an36045d
M3 - Article
AN - SCOPUS:84870884339
SN - 0003-2654
VL - 138
SP - 677
EP - 682
JO - Analyst
JF - Analyst
IS - 2
ER -