In situ bottom-up synthesis of porphyrin-based covalent organic frameworks

Elham Tavakol, Arvin Kakekhani, Shayan Kavani, Peng Tan, Mahdi Mohammadi Ghaleni, Mohsen Asle Zaeem, Andrew M. Rappe, Siamak Nejati

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Abstract

Synthesis and processing of two-or three-dimensional covalent organic frameworks (COFs) have been limited by solvent intractability and sluggish condensation kinetics. Here, we report on the electrochemical deposition of poly(5,10,15,20-tetrakis(4-aminophenyl)porphyrin)-covalent organic frameworks (POR-COFs) via formation of phenazine linkages. By adjusting the synthetic parameters, we demonstrate the rapid and bottom-up synthesis of COF dendrites. Both experiment and density functional theory underline the prominent role of pyridine, not only as a polymerization promoter but as a stabilizing sublattice, cocrystallizing with the framework. The crucial role of pyridine in dictating the structural properties of such a cocrystal (Py-POR-COF) is discussed. Also, a structure-to-function relationship for this class of materials, governing their electrocatalytic activity for the oxygen reduction reaction in alkaline media, is reported.

Original languageEnglish (US)
Pages (from-to)19560-19564
Number of pages5
JournalJournal of the American Chemical Society
Volume141
Issue number50
DOIs
StatePublished - Jan 1 2020

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ASJC Scopus subject areas

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

Cite this

Tavakol, E., Kakekhani, A., Kavani, S., Tan, P., Ghaleni, M. M., Zaeem, M. A., Rappe, A. M., & Nejati, S. (2020). In situ bottom-up synthesis of porphyrin-based covalent organic frameworks. Journal of the American Chemical Society, 141(50), 19560-19564. https://doi.org/10.1021/jacs.9b10787