Synthesis and properties of 5-aza-15-thiaporphyrins

• Yamashita, Daisuke

• Omori, Hiroto

• Fukui, Norihito

• Shinokubo, Hiroshi

Abstract

We have successfully prepared 5-aza-15-thiaporphyrin through nucleophilic sulfination of nitrogen-bridged dibromobisdipyrrin with sodium sulfide. X-ray diffraction analysis elucidated its structure in the solid state: two dipyrrin subunits were roughly coplanar around the sp^2-hybridized meso-nitrogen. In contrast, they adopted a folded conformation around the meso-sulfur atom. Due to its relatively distorted structure, 5-aza-15-thiaporphyrin shows weak antiaromaticity in the magnetic criteria. The sulfur atom was oxidized with m-chloroperbenzoic acid to provide 5-aza-15-thiaporphyrin S-dioxide in good yield. While 5-aza-15-thiaporphyrin was non-emissive, its S-dioxide exhibited fluorescence in solution.

Journal

• Journal of Porphyrins and Phthalocyanines

  Journal of Porphyrins and Phthalocyanines 24 (01n03), 84-89, 2020-03

  World Scientific

Keywords

• 5-aza-15-thiaporphyrin
• antiaromaticity
• heteroporphyrinoids
• sulfide
• sulfone

Details

• CRID: 1050285299779962368
• NII Article ID: 120006848966
• DOI: 10.1142/s108842461950069x
• ISSN: 10991409
• ISSN: 10884246
• HANDLE: 2237/00032321
• Web Site: https://nagoya.repo.nii.ac.jp/records/30135
• Web Site: https://www.worldscientific.com/doi/pdf/10.1142/S108842461950069X
• Text Lang: en
• Article Type: journal article
• Data Source:
  • IRDB
  • Crossref
  • CiNii Articles
  • KAKEN