Fluorescent anion sensors based on 4-amino-1,8-naphthalimide that employ the 4-amino N-H

The new charge neutral 4-amino-1,8-naphthalimide based anion sensors <b>2</b> and <b>3</b> bind to both acetate and dihydrogenphosphate with 1:1 stoichiometry through hydrogen bonding to both thiourea N–H atoms and in the case of dihydrogenphosphate, the naphthalimide 4 amino N–H group as well. This was clearly established from ¹H NMR titration experiments with <b>H₂PO₄</b>^-in DMSO-<i>d</i>₆ where a substantial shift in the resonance for the naphthalimide N–H was observed concomitant with the expected migration of the thiourea N–H chemical shifts. The binding constants determined from the titration studies indicate that the new sensors bind <b>H₂PO₄^- </b>more strongly than AcO⁻. Fluorescence titrations with sensor <b>3</b> indicate quenching of 59% and 36% upon addition of acetate and dihydrogenphosphate, respectively.