Fluorescent sensing of anions based on excited state intramolecular proton transfer in N-(3-hydroxy-

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A neutral N-amidothiourea-based excited state intramolecular proton transfer (ESIPT) anion receptor bearing an o-hydroxynaphthamide fluorophore and a thiourea binding site, N-(3-hydroxy-2-naphthamide)-N’-phenylthiourea (1a), was designed and synthesized. Fluorescence and absorption response of 1a toward anions were assessed in acetonitrile. IR and NMR experiments indicated that the “OH…O=C” intramolecular hydrogen bond (IHB) in 1a was weak so that it only exhibited the short-wavelength normal emission other than ESIPT fluorescence. Due to the high anion binding affinity of the N-amidothiourea binding site and the formation of a hydrogen binding network in the 1a-anion c omplex, 1a underwent structural change upon anion binding that strengthens the “OH…O=C” IHB, leading to the ESIPT and the observation of the long-wavelength ESIPT emission whereas the normal fluorescence is quenched. On the basis of NMR and fluorescence titrations and control experiments with model compounds, a sensing mechanism of the anion-binding-induced ESIPT was proposed. A neutral N-amidothiourea-based excited state intramolecular proton transfer (ESIPT) anion receptor bearing an o-hydroxynaphthamide fluorophore and a thiourea binding site, N- (3-hydroxy-2-naphthamide) -N’-phenylthiourea designed and synthesized. Fluorescence and absorption responses of 1a toward anions were assessed in acetonitrile. IR and NMR experiments indicated that the “OH ... O = C ” intramolecular hydrogen bond (IHB) in 1a was weak so that it only showed the short -wavelength normal emission other than ESIPT fluorescence. Due to the high anion binding affinity of the N-amidothiourea binding site and the formation of a hydrogen binding network in the 1a-anion complex, 1a underwent structural change upon anion binding that strengthens the “OH ... O = C ” IHB, leading to the ESIPT and the observation of the long-wavelength ESIPT emission while the normal fluorescence is quenched. On the basis of NMR and fluorescence titrations and control experiments with model compounds, a sensing mechanism of the anion-binding-induced ESIPT was proposed.
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