title: Control over charge separation in phthalocyanine-anthraquinone conjugates as a function of the aggregation status.
abstract: We have prepared three isomeric donor-acceptor systems, in which two phthalocyanine (Pc) units have been attached to the 1-,5- (1a), 1-,8- (1b), or 2-,6- (1c) positions of a central anthraquinone (AQ) moiety, leading to packed (1b) or extended (1a and 1c) topologies. The electronic interactions between the donor and the acceptor in the ground state or in the excited states have been studied by different electrochemical and photophysical techniques. Due to the markedly different topologies, we have been able to modify these interactions at the intramolecular level and, by a proper choice of the solvent environment, at the intermolecular level within aggregates. In triad 1b, the ZnPc units are forced to pi-stack cofacially and out of the plane of the AQ ring. Consequently, this molecule shows strong inter-Pc interactions that give rise to intramolecular excitonic coupling but a relatively small electronic communication with the AQ acceptor through the vinyl spacers. On the contrary, the 1-,5- or 2-,6-connections of triads 1a and 1c allow for an efficient pi-conjugation between the active units that extends over the entire planar system. These two molecules tend to aggregate in aromatic solvents by pi-pi stacking, giving rise to J-type oligomers. Photoexcitation of the Pc units of 1a-c results in the formation of the Pc.+-AQ.- charge transfer state. We have demonstrated that the kinetics of these electron transfer reactions is greatly dependent on the aggregation status of the triads.
authors.affiliation: Departamento de Química Organica, Facultad de Ciencias, Universidad Autónoma de Madrid, E-28049 Madrid, Spain.
authors.forename: Andreas
authors.initials: A
authors.lastname: Gouloumis
authors.forename: David
authors.initials: D
authors.lastname: González-Rodríguez
authors.forename: Purificación
authors.initials: P
authors.lastname: Vázquez
authors.forename: Tomás
authors.initials: T
authors.lastname: Torres
authors.forename: Shenggao
authors.initials: S
authors.lastname: Liu
authors.forename: Luis
authors.initials: L
authors.lastname: Echegoyen
authors.forename: Jeff
authors.initials: J
authors.lastname: Ramey
authors.forename: Gordon L
authors.initials: GL
authors.lastname: Hug
authors.forename: Dirk M
authors.initials: DM
authors.lastname: Guldi