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Updated: Jun 10, 2025

Synthesis and Characterization of Functionalized Metal-organic Frameworks
Published on: September 5, 2014
Room-Temperature Single-Phase Synthesis of Semiconducting Metal-Covalent Organic Frameworks With
Dongchuang Wu1,2, Qiongshan Zhang1, Shiyu Yin1
1Key Laboratory for Advanced Materials, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, 200237, China.
Abstract:
In order to improve the solubility of metallated monomers and product crystallinity, metal-covalent organic frameworks (MCOFs) are commonly prepared via high-temperature sol-vothermal synthesis. However, it hampers the direct extraction of crystallization evolution information. Exploring facile room-temperature strategies for both synthesizing MCOFs and exploiting the crystallinity mechanism is extremely desired. Herein, by a novel single-phase synthetic strategy, three MCOFs with different microstructure is rapidly prepared based on the Schiff base reaction between planarity-tunable C3v monomers and metallated monomers at room temperature. Based on detailed time-dependent experiments and theoretical calculations, it is found that there is a planarity-tuned and competitive growth relationship between disordered structures and crystal nucleus for the first time. The high planarity of monomers boosts the formation of crystal nucleus and rapid growth, suppressing the forming of amorphous structures. In addition, the microenvironment effect on selective photocatalytic coupling of benzylamine (BA) is investigated. The strong donor-acceptor (D-A) MCOF exhibits efficient photocatalytic activity with a high conversion rate of 99% and high selectivity of 99% in 5 h under the 520 nm light irradiation. This work opens a new pathway to scalable and efficient synthesis of highly crystalline MCOFs.

