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

摘要

We report the electrochemical properties,and electrogenerated chemiluminescence(ECL)of eight different organometallic complexes of Eu(III)and Tb(III),Eu(dbm)3phen,Eu(dbm)3bath,Eu(fod)3phen,Eu(tta)3phen,Tb(acac)3phen,Tb(acac)3bath,Tb(fod)3phen,and Tb(tmhd)3bpy in acetonitrile,where phen,bath,and bpy are 1,10-phenanthroline,bathophenanthroline,2,2’-bipyridyl,respectively,and the anionic ligands,acac~-,dbm~-,fod~-,and tta~-are the enolate forms of acetylacetone,dibenzoylmethanate,6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione,and thenoyltrifluoroacetone,respectively.The electronic states of the neutral and some charged states of the complexes were clarified with density functional theory calculations.The ECL spectra were recorded by using S2O8 ~(2-)as a coreactant,and for all complexes,sharp ECL spectra,which are attributable to the f-f transitions,were observed.On the potential-dependent ECL spectra,broad ECLs,which were originated from the ligands,were also detected.Based on the ECL behavior and the electronic states,the mechanisms of the intraconfigurational ECL were discussed.