Tripyrrin-armed isosmaragdyrins: Synthesis, heterodinuclear coordination, and protonation-triggered helical inversion

Chengjie Li, Kai Zhang, Masatoshi Ishida, Qizhao Li, Keito Shimomura, Glib Baryshnikov, Xin Li, Mathew Savage, Xin Yan Wu, Sihai Yang, Hiroyuki Furuta, Yongshu Xie

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Abstract

Oxidative ring closure of linear oligopyrroles is one of the synthetic approaches to novel porphyrinoids with dinuclear coordination sites and helical chirality. The spatial arrangement of the pyrrolic groups of octapyrrole (P8) affected the position of the intramolecular oxidative coupling of the pyrrolic units; tripyrrin-armed isosmaragdyrin analogue (1) containing a β,β-linked bipyrrole moiety was synthesized regioselectively in a high yield by using FeCl3. NiII-coordination at the armed tripyrrin site of 1 allowed the formation of diastereomeric helical twisted complexes (2A and 2B) and succeeding CuII-coordination at the macrocyclic core afforded heterodinuclear NiII/CuII-complexes (3A and 3B). Each of them comprised a pair of separable enantiomers, exhibiting P- and M-helices, respectively. Notably, diastereomeric interconversion from 2A to 2B was quantitatively achieved as a consequence of helical transformation under acidic conditions.

Original languageEnglish
Pages (from-to)2790-2795
Number of pages6
JournalChemical Science
Volume11
Issue number10
DOIs
Publication statusPublished - Mar 14 2020

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

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    Li, C., Zhang, K., Ishida, M., Li, Q., Shimomura, K., Baryshnikov, G., Li, X., Savage, M., Wu, X. Y., Yang, S., Furuta, H., & Xie, Y. (2020). Tripyrrin-armed isosmaragdyrins: Synthesis, heterodinuclear coordination, and protonation-triggered helical inversion. Chemical Science, 11(10), 2790-2795. https://doi.org/10.1039/c9sc06197e