Insights into the Photophysics and Supramolecular Organization of Congo Red in Solution and the Solid State

• Autor(a) principal: Costa, Ana L.
• Data de Publicação: 2017
• Outros Autores: Gomes, Ana C., Pillinger, Martyn, Gonçalves, Isabel S., Pina, João, Seixas de Melo, J. Sérgio
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
• Texto Completo: http://hdl.handle.net/10316/41708; https://doi.org/10.1002/cphc.201601236

Steady-state and time-resolved absorption and fluorescence measurements are reported for Congo Red (CR) in aqueous and dimethylsulfoxide (DMSO) solutions. The very low fluorescence quantum yield (≈10(-4) ) for CR in dilute solutions together with the absence of a triplet state indicates that internal conversion is the dominant deactivation route with more than 99.99 % of the quanta loss (attributed to the energy gap law for radiationless transitions). Although no direct evidence for trans-cis photoisomerization was obtained from absorption or fluorescence data, the global analysis of fs-transient absorption data indicates the presence of a photoproduct with a lifetime of ≈170 ps that is suggested to be associated with such a process. Spectral data for more concentrated CR solutions indicate the presence of oblique or twisted J-type aggregates. These results are compared with spectra for CR in the solid state (sodium salt) and intercalated in a layered double hydroxide via a one-step co-precipitation route. Powder XRD and electronic spectral data for the nanohybrid indicate that the CR guest molecules are intercalated as a monolayer consisting of slipped cofacial J-type aggregates.