title: Simultaneous control of emission localization and two-photon absorption efficiency in dissymmetrical chromophores.
abstract: The aim of the present work is to demonstrate that combined spatial tuning of fluorescence and two-photon absorption (TPA) properties of multipolar chromophores can be achieved by introduction of slight electronic chemical dissymmetry. In that perspective, two model series of structurally related chromophores have been designed and investigated. One is based on rod-like quadrupolar chromophores bearing either two identical or different electron-donating (D) end groups and the other on three-branched octupolar chromophores built from a trigonal donating moiety bearing identical or different acceptor (A) peripheral groups. The influence of the electronic dissymmetry is investigated by combined experimental and theoretical studies of the linear and nonlinear optical properties of dissymmetrical chromophores compared to their symmetrical counterparts. In both types of systems (i.e., quadrupoles and octupoles), experiments and theory reveal that excitation is essentially delocalized and that excitation involves synchronized charge redistribution (i.e., concerted intramolecular charge transfer) between the different D and A moieties within the multipolar structure. In contrast, the emission stems only from a particular dipolar subunit bearing the strongest D or A moiety due to fast excitation localization after excitation, prior to emission. Hence, control of emission characteristics (polarization and emission spectrum), can be achieved, in addition to localization, by controlled introduction of electronic dissymmetry (i.e., replacement of one of the D or A end-groups by a slightly stronger D' or A' unit). Interestingly, slight dissymmetrical functionalization of both quadrupolar and octupolar compounds does not lead to significant loss in TPA responses and can even be beneficial due to the spectral broadening and peak position tuning that it allows. This study thus reveals an original molecular engineering route allowing TPA enhancement in multipolar structures, due to concerted core-to-periphery or periphery-to-core intramolecular charge redistribution upon excitation, while providing for control of emission localization. Such a route could be extended to more intricate (dendritic) and multipolar (3D) systems.
authors.affiliation: CNRS, Chimie et Photonique Moléculaires (UMR 6510), 35042 Rennes, France.
authors.forename: Claudine
authors.initials: C
authors.lastname: Katan
authors.forename: Marina
authors.initials: M
authors.lastname: Charlot
authors.forename: Olivier
authors.initials: O
authors.lastname: Mongin
authors.forename: Céline
authors.initials: C
authors.lastname: Le Droumaguet
authors.forename: Viatcheslav
authors.initials: V
authors.lastname: Jouikov
authors.forename: Francesca
authors.initials: F
authors.lastname: Terenziani
authors.forename: Ekaterina
authors.initials: E
authors.lastname: Badaeva
authors.forename: Sergei
authors.initials: S
authors.lastname: Tretiak
authors.forename: Mireille
authors.initials: M
authors.lastname: Blanchard-Desce
mesh_terms: D000042:Absorption; D005453:Fluorescence; D008968:Molecular Conformation; D017785:Photons; D012997:Solvents / Q000737:chemistry; D013730:Terphenyl Compounds / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D012997:Solvents; D013730:Terphenyl Compounds; C550036:chromophore Q1; C550034:chromophore Q2; C550035:chromophore Q3