resumo
Supramolecularly organized host-guest systems have been synthesized by intercalating water-soluble forms of indigo (indigo carmine, IC) and thioindigo (thioindigo-5,5'-disulfonate, TIS) in zinc-aluminum-layered double hydroxides (LDHs) and zinc-layered hydroxide salts (LHSs) by coprecipitation routes. The colors of the isolated powders were dark blue for hybrids containing only IC, purplish blue or dark lilac for cointercalated samples containing both dyes, and ruby/wine for hybrids containing only TIS. The as-synthesized and thermally treated materials were characterized by Fourier transform infrared, Fourier transform Raman, and nuclear magnetic resonance spectroscopies, powder X-ray diffraction, scanning electron microscopy, and elemental and thermogravimetric analyses. The basal spacings found for IC-LDH, TIS-LDH, IC-LHS, and TIS-LHS materials were 21.9, 21.05, 18.95, and 21.00 angstrom, respectively, with intermediate spacings being observed for the cointercalated samples that either decreased (LDHs) or increased (LHSs) with increasing TIS content. UV-visible and fluorescence spectroscopies (steady-state and time-resolved) were used to probe the molecular distribution of the immobilized dyes. The presence of aggregates together with the monomer units is suggested for IC-LDH, whereas for TIS-LDH, IC-LHS, and TIS-LHS, the dyes are closer to the isolated situation. Accordingly, while emission from the powder H2TIS is strongly quenched, an increment in the emission of about 1 order of magnitude was observed for the TIS-LDH/LHS hybrids. Double-exponential fluorescence decays were obtained and associated with two monomer species interacting differently with cointercalated water molecules. The incorporation of both TIS and IC in the LDH and LHS hosts leads to an almost complete quenching of the fluorescence, pointing to a very efficient energy transfer process from (fluorescent) TIS to (nonfluorescent) IC.
palavras-chave
MAYA BLUE PIGMENT; CRYSTAL-STRUCTURE REFINEMENT; CO-INTERCALATION; SOLID-STATE; SEPIOLITE; ANIONS; PALYGORSKITE; HYDROTALCITE; CHROMOPHORES; COMPOSITE
categoria
Chemistry; Materials Science
autores
Costa, AL; Gomes, AC; Pereira, RC; Pillinger, M; Goncalves, IS; Pineiro, M; de Melo, JSS
nossos autores
Ana Catarina Costa Gomes Alves
Investigador Auxiliar
Ana Luísa Costa
Investigador
Isabel Maria de Sousa Gonçalves
Professor associado
Martyn Pillinger
Investigador Principalagradecimentos
We acknowledge funding by FEDER (Fundo Europeu de Desenvolvimento Regional) through COMPETE (Programa Operacional Factores de Competitividade). National funding through the FCT (Fundacao para a Ciencia e a Tecnologia) within the project Coimbra Chemistry Centre (PEst-OE/QUI/UI0313/2014) is thanked. This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT Ref. UID/CTM/50011/2013), financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. The FCT is acknowledged for a PhD grant to A.L.C. (ref. SFRH/BD/88806/2012) and a postdoctoral grant to A.C.G. (ref. SFRH/BPD/108541/2015).