Development of N-Benzamidothioureas as a New Generation of Thiourea-Based Receptors for Anion Recognition and Sensing

A series of neutral N-(substituted-benzamido)-N'-phenylthioureas (substituent = p-OC(2)H(5), p-CH(3), m-CH(3), H, p-Cl, p-Br, m-Cl, and p-NO(2)) were designed as anion receptors, in which the thiourea binding site was attached to the benzamido moiety via an N-N bond. The absorption spectra of these N-benzamidothioureas in acetonitrile peaked at ca. 270 nm were found to show unprecedented red shifts by 7 373 to 14 325 cm(-1) in the presence of anions such as AcO(-), F(-), and H(2)PO(4)(-). Under the same conditions, the classic neutral thiourea receptors, N-(substituted-phenyl)-N'-phenylthioureas, showed absorption spectral shifts in most cases of less than 800 cm(-1) with one exception of 6501 cm(-1). Control experiments, effects of protic solvent, and (1)H NMR titration confirmed the formation of hydrogen-bonding complexes between the new N-benzamidothiourea receptors and anions. The binding constants with AcO(-), for example, are at 10(5)-10(7) mol(-1) L order of magnitude, which are 13 to 590 times those of the corresponding classic N-phenylthioureas in the same solvent. It was found that, whereas the absorption of the N-benzamidothiourea receptors showed essentially no dependence on the substituent, the substantially red-shifted new absorption band of the N-benzamidothiourea-anion binding complex was sensitively subject to the substituent. A linear relationship was found between the absorption energies of the N-benzamidothiourea-acetate binding complexes and the Hammett constants of the substituents with a negative slope of -0.34 eV. This led to the assignment that the substantially red-shifted absorption band was the ground-state intramolecular charge-transfer absorption with the substituent locating in the electron acceptor moiety. It was concluded that anion binding to the thiourea moiety of the N-benzamidothiourea receptors switched on their ground-state charge transfer. An anion-binding induced structural change was suggested to occur around the N-N bond in N-benzamidothioureas, which resulted in a substantially increased electron donating ability of the electron donor in the receptor molecules. As a consequence, the ground-state charge transfer takes place in the N-benzamidothiourea-anion binding complexes, leading to unprecedented red shifts in the absorption spectra and substantially enhanced anion binding affinities than those of the corresponding N-phenylthiourea receptors. N-Benzamido-N'-phenylthioureas represent a new generation of neutral thiourea-based anion receptors that show substantially improved anion binding performance important for anion sensing and recognition.