New fluorescence PET systems based on N2S2 pyridine-anthracene-containing macrocyclic ligands.: Spectrophotometric, spectrofluorometric, and metal ion binding studies

Three new fluorescent devices for protons and metal ions have been synthesized and characterized, and their photophysical properties have been explored; these are the macrocycles 7-(9-anthracenylmethyl)-3,11-dithia-7,17-diazabicyclo[11.3.1]heptadeca-1(17),13,15-triene (L1) and 7-(10-methyl-9-anthracenylmethyl)-3,11-dithia-7,17-diazabicyclo[11.3.1]heptadeca-1(17),13,15-triene (L2) and the bis macrocycle 7,7'-[9,10-anthracenediylbis(methylene)]bis-3,11-dithia-7,17-diazabicyclo[11.3.1]heptadeca-1 (1 7),13,15-triene (0). All these systems have a pyridil-thioether-containing macrocycles as a binding site and an anthracene moiety as a signaling agent. The coordination properties of these ligands toward Cu(II), Co(II), Ni(II), Zn(II), and Pd(II) have been studied in solution and in the solid state. The addition of these metal ions to dichloromethane solutions of L1, L2, and L3 produce strong changes in the absorption and emission spectra of these ligands. The stoichiometry of the species, formed at 298 K, have been determined from absorption and fluorescence titrations. The Co(II) and Cu(II) complexes of L1 have been studied by EPR spectroscopy. This last complex and its free ligand have also been characterized by X-ray crystallography.