Aromatic molecules in restricted geometries: pyrene excimer formation in an anchored bilayer

The galleries of an anionic clay, Mg-Al Layered Double Hydroxide (Mg-Al LDH) have been functionalized by intercalating the anionic surfactant do-decyl sulfate. Within the galleries, the alkyl chains of the surfactant adopt a bilayer structure with the sulfate headgroup anchored to the inorganic sheet. Pyrene molecules have been solubilized in the anchored bilayer by partitioning from polar solvents. The presence of pyrene molecules induces conformational disorder in the alkyl chains of the bilayer and more importantly inhibits the rotational disordering motion of the sulfate headgroup. Pyrene fluorescence indicates formation of excimers whose intensity increases with concentration of solubilized pyrene indicating that they are mobile. Pyrene solubilized in the anchored bilayer exhibits unusual phenomena; on evacuation the excimer band disappear but reappears on releasing vacuum. It is shown that this behavior arises due to the loss of water of hydration of the headgroup on evacuation and as a consequence the pyrene moves into the less polar interior of the bilayer where it is immobile and can no longer diffuse and form excimers. The motion of pyrene into the interior of the bilayer creates free space near the surfactant chain termini, which manifests in the disappearance of the methyl-rocking mode of the ordered (-tt) end-chain conformer in the Raman spectra.