Electrochemiluminescence from Os(phen)2(dppene)2+(phen = 1,10-phenanthroline and dppene = bis(diphenylphosphino)ethene)

Abstract

The electrochemiluminescence (ECL) of Os(phen)2(dppene)2+ (phen = 1,10-phenanthroline and dppene = bis(diphenylphosphino)ethene) is reported in mixed CH3CN/H2O (50:50 v/v) and aqueous (0.1 M KH2PO4) solutions with tri-n-propylamine (TPrA) as an oxidative-reductive coreactant. ECL efficiencies (φecl = photons emitted/redox event) of 2.0 in aqueous, and 0.95 in mixed for Os(phen)2(dppene)2+ were obtained using Ru(bpy)32+ (bpy = 2,2‘-bipyridine) as a relative standard (φecl = 1). Photoluminescence (PL) efficiencies of 0.094 and 0.053 were obtained in aqueous and mixed solutions, respectively, as compared to Ru(bpy)32+ (φem = 0.042). The ECL spectra were identical to photoluminescence spectra (λmax ≅ 584 nm), indicating formation of the same metal-to-ligand (MLCT) excited states in both ECL and PL. The ECL is linear over several orders of magnitude in aqueous and mixed solution, with theoretical detection limits (blank plus three times the standard deviation of the noise) of 16.9 nM in H2O and 0.29 nM in CH3CN/H2O (50:50 v/v).

Department(s)

Chemistry and Biochemistry

Document Type

Article

DOI

https://doi.org/10.1021/ac020089m

Keywords

solution chemistry, ligands, photoluminescence, solvents, osmium

Publication Date

2002

Journal Title

Analytical chemistry

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