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Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks

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Published on: February 10, 2023

Towards single-crystalline two-dimensional poly(arylene vinylene) covalent organic frameworks.

Shaik Ghouse¹, Ziang Guo^2,3, Sergio Gámez-Valenzuela^4,5

¹Faculty of Chemistry and Food Chemistry and Center for Advancing Electronics Dresden, Technische Universität Dresden, Dresden, Germany.

Nature Chemistry

|January 20, 2026

Summary

A new Mannich-elimination strategy creates highly crystalline 2D poly(arylene vinylene)s (2D PAVs). This method improves polymer semiconductor properties for electronics and catalysis by enhancing charge transport.

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Synthesis and Characterization of Functionalized Metal-organic Frameworks

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Published on: September 5, 2014

Area of Science:

Materials Science
Polymer Chemistry
Organic Electronics

Background:

2D conjugated polymers, specifically 2D poly(arylene vinylene)s (2D PAVs), show potential in optoelectronics, photocatalysis, and electrochemistry.
Conventional synthesis methods often yield poorly crystalline or inaccessible 2D PAVs, limiting their performance.

Purpose of the Study:

To develop a novel strategy for synthesizing highly crystalline 2D PAVs with precise crystallization control.
To investigate the impact of crystallinity on the charge transport properties of 2D PAVs.

Main Methods:

A Mannich-elimination strategy was employed to convert 2D imine-covalent organic frameworks into 2D PAVs via reversible C=C bond formation.
Techniques including high-resolution transmission electron microscopy and continuous rotation electron diffraction were used for structural characterization.
Charge transport properties were measured and compared between crystalline and amorphous 2D PAVs.

Main Results:

The Mannich-elimination strategy successfully produced 11 highly crystalline 2D PAVs with diverse lattice structures (honeycomb, square, kagome).
The synthesized 2D PAVs exhibited high specific surface areas (up to ~2,000 m² g⁻¹) and significant lattice-mismatch tolerance.
Benzotrithiophene-based 2D PAVs demonstrated charge mobilities ten times higher than their amorphous counterparts.

Conclusions:

The Mannich-elimination approach provides a versatile route to robust, highly crystalline 2D conjugated polymer materials.
Crystallinity is a critical factor in determining charge transport efficiency in 2D PAVs.
This work paves the way for advanced applications of 2D conjugated polymers in various fields.