Gemini-Porphyrazines: The synthesis and characterization of metal-capped cis- and trans-porphyrazine tetrathiolates

John W. Sibert, Theodore F. Baumann, David J. Williams, Andrew J.P. White, A. G.M. Barrett*, Brian M. Hoffman

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

22 Scopus citations


Peripherally-functionalized porphyrazines of the form M[pz(A(n):B(4-n))] (inset 1), where A and B symbolize functional moieties (e.g., a-d in Table 1) fused directly to the β-positions of the pyrroles, have the potential to serve in a wide range of applications. Previously, we reported the synthesis of porphyrazine di- and octathiolate ligands, M[pz(b3:c1)] and M[pz(c4)], respectively, where b is a fused benzo ring and c represents two thiolates fused at the β-pyrrole positions to form a dithiolene capable of the peripheral chelation of a metal ion. We describe here a general strategy that solves the more difficult problem of preparing and isolating the porphyrazinetetra- and hexathioethers and the porphyrazinetetra- and hexathiolates, with the focus being the trinuclear metal complexes of the trans- and cis-porphyrazinetetrathiolate isomers (trans- and cis-M[pz(b2:d2)]), denoted as gemini porphyrazines. Spectroscopic and electrochemical studies reveal that the physical properties of the cis- and trans-tetrathioether porphyrazines exhibit intriguing differences associated with their distinct molecular symmetries. These functionalized macrocycles have been used to prepare the trans- and cis-gemini porphyrazines 14 and 16, the two isomeric porphyrazinetetrathiolate macrocycles that are peripherally-metalated with two bis(triethylphosphine)platinum(II) moieties. The X-ray structure of the trans isomer, 14, is presented; it is the first structure of a porphyrazine or phthalocyanine having a trans-type substitution pattern.

Original languageEnglish (US)
Pages (from-to)10487-10493
Number of pages7
JournalJournal of the American Chemical Society
Issue number43
StatePublished - Oct 30 1996

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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