A Modular Synthesis of Planar, Redox-Stable Hückel Anti-Aromatic [36]Nonaphyrin (1.0.0.1.0.0.1.0.0) with Only Three <i>meso</i>-Bridges
A rigid dithienopyrrole (DTP) subunit was functionalized by taking advantage of the fused core, which upon Lewis acid-catalyzed self-condensation afforded two structurally distinct expanded porphyrinoids, namely [36]nonaphyrin (<b>S</b><sub><b>6</b></sub><b>N</b><sub><b>3</b></sub>) and [48]dodecaphyrin (<b>S</b><sub><b>8</b></sub><b>N</b><sub><b>4</b></sub>). The single crystal X-ray structure of <b>S</b><sub><b>6</b></sub><b>N</b><sub><b>3</b></sub> revealed a perfectly planar conformation. Various spectroscopic and DFT analyses unambiguously confirmed the strong anti-aromatic feature of <b>S</b><sub><b>6</b></sub><b>N</b><sub><b>3</b></sub>, and the large expanded congener <b>S</b><sub><b>8</b></sub><b>N</b><sub><b>4</b></sub> displayed a nonplanar conformation with weak anti-aromaticity.
Authors
- Shigeki Mori (ORCID: https://orcid.org/0000-0001-6731-2357)
- Thondikkal Sulfikarali (ORCID: https://orcid.org/0000-0002-5563-5324)
- Sabapathi Gokulnath (ORCID: https://orcid.org/0000-0001-9299-5217)
- Aathira Edwin (ORCID: https://orcid.org/0000-0003-0425-8116)
- Jayaprakash Ajay (ORCID: https://orcid.org/0000-0003-0525-9970)
- Meghna Sasi
Institutions
- Ehime University (JP)
- Indian Institute of Science Education and Research Thiruvananthapuram (IN)
Publication Details
- Journal
- Organic Letters
- Published
- 2025-02-21
- DOI
- https://doi.org/10.1021/acs.orglett.5c00170
- Citations
- 1
- Primary Topic
- Porphyrin and Phthalocyanine Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.52
Funders
- Department of Science and Technology, Ministry of Science and Technology, India
- Council of Scientific and Industrial Research, India
- Science and Engineering Research Board