Bis(carbazolyl)ureas as selective receptors for the recognition of hydrogenpyrophosphate in aqueous media

Recognition properties of the novel bis(carbazole) tris-ureidic-based receptors 1 and 2 toward different anions have been studied by (1)H NMR and absorption and emission spectroscopy, as well as by DFT calculations. Receptor 1, in which the two urea-functionalized arms are decorated with p-nitrophenyl rings, behaves as a highly selective chromogenic molecular probe for hydrogenpyrophosphate anion in a competitive medium (acetonitrile/water, 70/30). Receptor 2, bearing two urea arms decorated with photoactive pyrenyl rings, acts as a highly selective fluorescent molecular probe for hydrogenpyrophosphate anion in either acetonitrile or an aqueous mixture (acetonitrile/water, 85/15). Receptor 2 exhibits a dual monomer-excimer emission spectrum and undergoes a remarked ratiometry in acetonitrile in the presence of hydrogenpyrophosphate: the excimer band disappears, whereas the monomer band is slightly increased. However, in the aqueous mixture, a strong increase of the excimer emission band was observed, while the monomer emission bands remained almost unaffected. The resulting binding modes and spectroscopic features are explained by suitable structures of model complexes for both receptors. In such complexes, a peripheral cooperative effect was found, alleviating the excess of negative charge in the guest toward the outer surface of the host, as well as the required enlargement on its internal cavity.