Design, synthesis and photophysical studies of simple fluorescent anion PET sensors using charge neutral thiourea receptors

Abstract

The synthesis of four fluorescent photoinduced electron transfer (PET) chemosensors 1–4 for anions is described. These are all based on a simple design employing charge neutral aliphatic or aromatic thiourea anion receptors connected to an anthracene fluorophore via a methylene spacer. Here the anion recognition occurred through 1 : 1 hydrogen bonding between the thiourea protons and the anion, as demonstrated by observing the changes in the ¹H NMR in DMSO-d₆ where the two thiourea protons were shifted downfield upon addition of anions. Whereas 1–3 were designed for the detection of anions such as fluoride, acetate or phosphate, 4 was made for the recognition of N-protected amino acids. All the sensors showed ‘ideal’ behaviour where only the fluorescence emission was quenched upon anion recognition, due to enhanced efficiency of electron transfer quenching from the receptor to the excited state of the fluorophore. By simply varying the nature of the thiourea substituent it was possible to modulate, or tune, the acidity of the thiourea receptor moiety, altering the sensitivity of the anion recognition. For 1, the anion selectivity and the degree of the fluorescence quenching were in the order of F⁻ > AcO⁻ > H₂PO₄⁻, with Cl⁻ or Br⁻ not being detected.