Syntheses of Water-Soluble Silver(II)-Phthalocyanines toward Optical Sensing for Thiol Detection

Water-soluble silver(II)-phthalocyanine complexes (AgPcs), tetrakis{4-(N-alkylpyridinium)thio}phthalocyaninato silver(II) tetrafluoroborate, [Ag(tRpySpc)](BF4)4, (R = Me and Et), have been synthesized for the first time by quaternization of pyridyl groups of tetrakis(4-pyridylthio)phthalocyaninato silver(II) by using Meerwein reagents and characterized by ESI-MS, elemental analyses, and optical absorption spectroscopy. Although they strongly aggregate in water, the presence of appropriate surfactants, such as polyethyleneglycol-monooleyl ether (n = approximately 50; PEG50) and sodium dodecyl sulfate, effectively disaggregates them to monomeric species. The spectral properties of the AgPcs and their aggregates in aqueous and nonaqueous solutions have been investigated by optical absorption, emission, and magnetic circular dichroism spectroscopy. These AgPcs rapidly react with thiols such as cysteine, glutathione, homocysteine, and sodium 2-sulfanylethanesulfonate (even on the order of 0.01 mM) in aqueous PEG50 solutions at room temperature to liberate the corresponding macrocyclic ligand, H2Pc, but not with the other amino-acid analogs without sulfhydryl groups. The molar ratio of thiol to AgPc has been determined to be 1:1. Since AgPcs are essentially nonfluorescent at room temperature, while H2Pcs emit intense red fluorescence, AgPcs can be a potent thiol-sensor toward bioimaging.