Three-Dimensional Fully Conjugated Carbaporphyrin Cage

Xian Sheng Ke, Taeyeon Kim, Qing He, Vincent M. Lynch, Dongho Kim, Jonathan L. Sessler

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45 Citations (Scopus)


A fully conjugated three-dimensional (3D) expanded carbaporphyrin (2) was prepared in a one-pot procedure that involves a [2+4] condensation reaction between a dibenzo[g,p]chrysene-bearing tetrapyrrole precursor (1) and pentafluorobenzaldehyde, followed by oxidation. Single crystal X-ray diffraction analysis revealed that 2 possesses a cage-like structure consisting of four dipyrromethenes and two bridging dibenzo[g,p]chrysene units. As prepared, 2 is nonaromatic as inferred from UV-vis-NIR and 1 H NMR spectroscopy and a near-zero (1.75) nucleus-independent chemical shift (NICS) value. In contrast, after protonation with trifluoroacetic acid (TFA), the cage gains global aromatic character as inferred from the large negative NICS value (11.63) and diatropic ring current observed in the anisotropy of the induced current density (ACID) plot, as well as the ca. 8-fold increase in the excited state lifetime. In addition, the size of the cavity increases to ca. 143 Å 3 upon protonation as deduced from a single crystal X-ray diffraction analysis. To our knowledge, this is the largest carbaporphyrin prepared to date and the first with a fully conjugated 3D cage structure whose size and electronic features may be tuned through protonation.

Original languageEnglish
Pages (from-to)16455-16459
Number of pages5
JournalJournal of the American Chemical Society
Issue number48
Publication statusPublished - 2018 Dec 5

Bibliographical note

Publisher Copyright:
© 2018 American Chemical Society.

All Science Journal Classification (ASJC) codes

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


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