title: Controlling the fluorescence behavior of 1-pyrenesulfonate by cointercalation with a surfactant in a layered double hydroxide.
abstract: Zn-Al layered double hydroxides (LDHs) containing solely 1-pyrenesulfonate (PS) or 1-heptanesulfonate (HS) anions, or a mixture of the two with HS/PS molar ratios ranging between ca. 7.5 and 82, were prepared by the direct synthesis method and characterized by powder X-ray diffraction, thermal and elemental analyses, scanning electron microscopy, and FT-IR, FT-Raman, and (13)C{(1)H} CP MAS NMR spectroscopies. Well-ordered intercalates were obtained with basal spacings of 18.8 Å for the LDH intercalated by PS and 19.2-19.4 Å for the other materials containing HS. The photophysics of the solids, as well as the PS probe dissolved in water and common organic solvents (aiming to compare the behavior of the "isolated" molecule with that in the solid), were investigated by steady-state and time-resolved fluorescence techniques. The fluorescence spectra of the solid samples display two bands with maxima at 376 and 495 nm. Depending on the HS/PS ratios, the band intensity ratio (obtained at 375 and 520 nm) changes, reflecting different contributions from monomer and dimer species. The decays collected at 375 nm are biexponentials with a major component (∼97% of the total fluorescence) of 105 ns for the highest HS/PS ratio, which further loses importance with an increase in the PS content. When the decays are collected at 480 and 520 nm, the fits are triexponentials with a major component varying from 108 to 124 ns, attributed to an excimer. Steady-state and time-resolved measurements with PS in solution (ethanol, methanol, DMF, DMSO, and water) were also measured, and a comparison of the vibronic I1/I3 ratio and lifetimes in water (65 ns) with those in the LDHs indicates that the PS probe in the cointercalated LDHs is surrounded by the HS surfactant.
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.
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.
authors.forename: J Sérgio
authors.initials: JS
authors.lastname: Seixas de Melo