Electrogenerated Chemiluminescence. 58. Ligand-Sensitized Electrogenerated Chemiluminescence in Europium Labels

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Abstract
The electrochemistry and electrogenerated chemiluminescence (ECL) of a series of europium chelates, cryptates, and mixed-ligand chelate/cryptand complexes were studied. The complexes were of the following general forms: EuL(4)(-), where L = β-diketonate, a bis-chelating ligand (such as dibenzoylmethide), added as salts (A)EuL(4), where A = tetrabutylammonium ion or piperidinium ion (pipH(+)); Eu(crypt)(3+), where crypt = a cryptand ligand, e.g., 4,7,13,16,21-pentaoxa-1,10-diazabicyclo[8,8,5]tricosane; and Eu(crypt)(L)(2+) for the mixed-ligand systems. ECL was obtained for the chelates and mixed-ligand systems by reducing the complexes at a Pt electrode in the presence of peroxydisulfate in acetonitrile solutions and was attributed to the electron-transfer reaction between the reduced bound ligands and SO(4)(•)(-), followed by intramolecular excitation transfer from the excited ligand orbitals to the metal-centered 4f states. No ECL was observed under the same conditions for the europium complexes incorporating only the cryptand ligands in aqueous solution. The ECL spectra matched the photoluminescence spectra with a narrow emission band observed at 612 nm, corresponding to a metal-centered 4f-4f transition. The ECL efficiencies for the ECL-active species were low, about 10(-)(1)-10(-)(4)% of that of the Ru(bpy)(3)(2+)/S(2)O(8)(2)(-) system under similar conditions.