Synthesis and study of the use of heterocyclic thiosemicarbazones as signaling scaffolding for the recognition of anions.

A family of heterocyclic thiosemicarbazone dyes (1-9) linked to different furan, thiazole, (bi)thiophene, and arylthiophene pi-conjugated bridges were synthesized in good yields, and their response toward anions was studied. Acetonitrile solutions of 1-9 show bands in the 326-407 region that are modulated by the electron-donor or -acceptor strength of the heterocyclic systems appended to the phenylthiosemicarbazone moiety. Anions of different shape such as fluoride, chloride, bromide, iodide, dihydrogen phosphate, hydrogen sulfate, nitrate, acetate, cyanide, and thiocyanate were employed for the recognition studies. From these anions, only fluoride, cyanide, acetate, and dihydrogen phosphate displayed sensing features. Two different effects were observed, (i) a low bathochromic shift of the absorption band due to coordination of the anions with the thiourea protons and (ii) the growth of a new red-shifted band with a concomitant change of the solution from yellow or pale yellow to orange-red due to deprotonation. The extent of each process is a balance between the acidity tendency of the thioureido-NH donors modulated by the donor or acceptor groups in the structure of the receptors and the basicity of the anions. Fluorescence studies were also in agreement with the different effects observed on the UV/vis titrations. Stability constants for the two processes (complex formation + deprotonation) for selected receptors and the anions fluoride and acetate were determined spectrophotometrically using the program HYPERQUAD. Semiempirical calculations to evaluate the hydrogen-donating ability of the dyes and (1)H NMR titrations experiments with fluoride were carried out. A prospective electrochemical characterization of compound 3 in the presence of anions was also performed.