In Situ Bottom-up Synthesis of Porphyrin-Based Covalent Organic Frameworks

Elham Tavakoli; Arvin Kakekhani; Shayan Kaviani; Peng Tan; Mahdi Mohammadi Ghaleni; Mohsen Asle Zaeem; Andrew M Rappe; Siamak Nejati

doi:10.1021/jacs.9b10787

In Situ Bottom-up Synthesis of Porphyrin-Based Covalent Organic Frameworks

J Am Chem Soc. 2019 Dec 18;141(50):19560-19564. doi: 10.1021/jacs.9b10787. Epub 2019 Dec 9.

Authors

Elham Tavakoli¹, Arvin Kakekhani², Shayan Kaviani³, Peng Tan^{2

4}, Mahdi Mohammadi Ghaleni³, Mohsen Asle Zaeem⁵, Andrew M Rappe², Siamak Nejati^{1

3}

Affiliations

¹ Department of Mechanical and Materials Engineering , University of Nebraska-Lincoln , Lincoln , Nebraska 68588-8286 , United States.
² Department of Chemistry , University of Pennsylvania , Philadelphia , Pennsylvania 19104-6323 , United States.
³ Department of Chemical and Biomolecular Engineering , University of Nebraska-Lincoln , Lincoln , Nebraska 68588-8286 , United States.
⁴ Department of Physics , Harbin Institute of Technology , Harbin 150001 , China.
⁵ Department of Mechanical Engineering , Colorado School of Mines , Golden , Colorado 80401-1887 , United States.

PMID: 31801014
DOI: 10.1021/jacs.9b10787

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.