Preparation of polyetherol-appended sulfur porphyrazines and investigations of peripheral metal ion binding in polar solvents

We describe the complete synthesis and characterization of a new family of peripherally functionalized porphyrazines (pz's) with four, three, or two ( in a trans conformation) bis[thioethoxy(ethoxy)ethanol] moieties appended a t the pyrroles. These "polyetherol" groups serve as weak exocyclic binding sites for a number of metal ions and also provide solubility of the pz's in low molecular-weight alcohols and water. Electronic spectra of the modifie d porphyrazines exhibit distinct changes in the visible region (both absorb ance and fluorescence) in response to treatment with Ag+, Pb2+: Cd2+, Cs+, and Ni2+ in solution. Such properties make these compounds intriguing candi dates for incorporation into the transducer layers in optically based chemi cal sensors.