title: Efficient greenish blue electrochemiluminescence from fluorene and spirobifluorene derivatives.
abstract: The spectroscopic and electrochemical behavior as well as electrogenerated chemiluminescence (ECL) of a series of donor-π-donor derivatives bearing triphenylamine groups as donor connected to a fluorene, 2,7-bis-(4-(N,N-diphenylamino)phen-1-yl)-9,9'-dimethylfluorene (1), or spirobifluorene core, 2,7-bis-(4-(N,N-diphenylamino)phen-1-yl)-9,9'-spirobifluorene (2) and 2,2',7,7'-tetrakis(4-(N,N-diphenylamino)phen-1-yl)-9,9'-spirobifluorene (3), were investigated. Besides a high photoluminescence (PL) quantum yield in solution (between 81 and 87%), an efficient radical ions annihilation process induces intense greenish blue ECL emission that could be seen with the naked eye. Only the tetrasubstituted spirobifluorene derivative (compound 3) shows weak ECL obtained by a direct annihilation mechanism. Because the energy of the annihilation reaction is higher than the energy required to form the singlet excited state, the S-route could be considered the pathway followed by the ECL process in these molecules. The ECL emissions recorded by direct ion-ion annihilation show two bands compared to the single structureless PL band. The ECL spectra obtained by a coreactant approach using benzoylperoxide  as a coreagent show no differences relative to that produced by annihilation, except for an increasing of ECL intensity for all compounds.
authors.affiliation: Physikalisches Institut, Westfälische Wilhelms-Universität, Heisenbergstrasse 11, D-48149 Münster, Germany. federico.polo@unipd.it
authors.forename: Federico
authors.initials: F
authors.lastname: Polo
authors.forename: Fabio
authors.initials: F
authors.lastname: Rizzo
authors.forename: Manoel
authors.initials: M
authors.lastname: Veiga-Gutierrez
authors.forename: Luisa
authors.initials: L
authors.lastname: De Cola
authors.forename: Silvio
authors.initials: S
authors.lastname: Quici