title: An Indigo Carmine-Based Hybrid Nanocomposite with Supramolecular Control of Dye Aggregation and Photobehavior.
abstract: Zn-Al layered double hydroxides (LDHs) containing solely indigo carmine (IC) or 1-hexanesulfonate (HS) anions, or a mixture of the two with different HS/IC molar ratios, were prepared by the direct synthesis method and characterized by various techniques. Hydrotalcite-type phases were obtained with basal spacings of 17.6 Å for the LDH intercalated by IC (IC-LDH) and 18.2-18.3 Å for the other materials containing HS. From the basal spacing for IC-LDH and UV/Vis spectroscopic data, it is proposed that the dye molecules assemble within the interlayer galleries to form a J-type stacking arrangement. A comprehensive electronic spectral and photophysical study was undertaken for IC in solution and all materials, aiming to obtain a detailed characterization of the host-guest and guest-guest interactions. In solution (the solvent surrounded "isolated" molecule), IC presents a fast excited state proton transfer with rate constants of ∼1.2-1.4×10(11)  s(-1) , which is linked to the very efficient radiationless deactivation channel. In the solid state it is shown that incorporation of IC within the LDH decreases the level of aggregation, and that further addition of HS induces the appearance of isolated IC units within the LDH galleries. The indigo carmine-based nanocomposites reported constitute a step forward in the design of hybrid materials with tunable properties.
authors.affiliation: Coimbra Chemistry Centre, Department of Chemistry, University of Coimbra, Rua Larga, 3004-535 Coimbra (Portugal).|Department of Chemistry, CICECO - Aveiro Institute of Materials, University of Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro (Portugal).
authors.forename: Ana L
authors.initials: AL
authors.lastname: Costa
authors.affiliation: Department of Chemistry, CICECO - Aveiro Institute of Materials, University of Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro (Portugal).
authors.forename: Ana C
authors.initials: AC
authors.lastname: Gomes
authors.affiliation: Department of Chemistry, CICECO - Aveiro Institute of Materials, University of Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro (Portugal). mpillinger@ua.pt.
authors.forename: Martyn
authors.initials: M
authors.lastname: Pillinger
authors.affiliation: Department of Chemistry, CICECO - Aveiro Institute of Materials, University of Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro (Portugal).
authors.forename: Isabel S
authors.initials: IS
authors.lastname: Gonçalves
authors.affiliation: Coimbra Chemistry Centre, Department of Chemistry, University of Coimbra, Rua Larga, 3004-535 Coimbra (Portugal). sseixas@ci.uc.pt.
authors.forename: J Sérgio Seixas
authors.initials: JS
authors.lastname: de Melo
keywords: aggregation; host-guest systems; indigo carmine; layered compounds; photophysics