Interlayer Interactions As Design Tool for Large-Pore COFs

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2021 Sep 8

PMID 34495671

Citations 12

Authors

Sebastian T Emmerling

Robin Schuldt

Sebastian Bette

Liang Yao

Robert E Dinnebier

Johannes Kastner

Bettina V Lotsch

Affiliations

Soon will be listed here.

Abstract

Covalent organic frameworks (COFs) with a pore size beyond 5 nm are still rarely seen in this emerging field. Besides obvious complications such as the elaborated synthesis of large linkers with sufficient solubility, more subtle challenges regarding large-pore COF synthesis, including pore occlusion and collapse, prevail. Here we present two isoreticular series of large-pore imine COFs with pore sizes up to 5.8 nm and correlate the interlayer interactions with the structure and thermal behavior of the COFs. By adjusting interlayer interactions through the incorporation of methoxy groups acting as pore-directing "anchors", different stacking modes can be accessed, resulting in modified stacking polytypes and, hence, effective pore sizes. A strong correlation between stacking energy toward highly ordered, nearly eclipsed structures, higher structural integrity during thermal stress, and a novel, thermally induced phase transition of stacking modes in COFs was found, which sheds light on viable design strategies for increased structural control and stability in large-pore COFs.

Citing Articles

Dimensional evolution of charge mobility and porosity in covalent organic frameworks.

Fu S, Li X, Wen G, Guo Y, Addicoat M, Bonn M Nat Commun. 2025; 16(1):2219.

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The Devil Is in the Details: Pitfalls and Ambiguities in the Analysis of X-ray Powder Diffraction Data of 2D Covalent Organic Frameworks.

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