Synthesis and coordination chemistry of unsymmetrical tetraazaporphyrins containing single oxathia- and thiacrown substituents

Singly crowned porphyrazines containing oxathia- and thiacrown ethers were prepared from a mixed condensation of 1,2-dicyanobenzene or its 3,4-dibutyl analog and the appropriate crowned maleonitrile precursor. Peripheral meta l-binding to each porphyrazine was examined spectrophotometrically. The oxa thiaether-crowned porphyrazines were found to coordinate Ag(I) and HgCl2, t hough all complexes suffered from poor solubility and complexes with the la tter were unstable in polar media. With an interest in the formation of com paratively more stable and soluble heavy and transition metal complexes, tw o new sets of thiaether-crowned porphyrazines were examined. In these cases , coordination of Hg(II), Ag(I), Cu(I) and Cu(FZ) was observed with no evid ence for complexation of Tl(I), Pb(II) or CdCl2. (C) 2000 Elsevier Science Ltd. All rights reserved.