Unprecedented Application of Covalent Organic Frameworks for Polymerization Catalysis: Rh/TPB-DMTP-COF in Polymerization of Phenylacetylene and Its Functional Derivatives

Qingbin Cao; Shaowen Zhang; Li Zhang; Fei Gao; Jupeng Chen; Yuping Dong; Xiaofang Li

doi:10.1021/acsami.1c00512

Unprecedented Application of Covalent Organic Frameworks for Polymerization Catalysis: Rh/TPB-DMTP-COF in Polymerization of Phenylacetylene and Its Functional Derivatives

ACS Appl Mater Interfaces. 2021 Mar 24;13(11):13693-13704. doi: 10.1021/acsami.1c00512. Epub 2021 Mar 12.

Authors

Qingbin Cao¹, Shaowen Zhang¹, Li Zhang¹, Fei Gao¹, Jupeng Chen¹, Yuping Dong², Xiaofang Li¹

Affiliations

¹ Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, 5 South Zhongguancun Street, Haidian District, Beijing 100081, China.
² Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China.

PMID: 33709703
DOI: 10.1021/acsami.1c00512

Abstract

Covalent organic frameworks (COFs) are applied widely in organic catalysis; however, no precedent has been reported in polymerization catalysis. Herein, we report the new application of COFs for polymerization catalysis. Different amounts of homogeneous Rh catalyst are incorporated into the COF via post-treatment to give a series of TPB-DMTP-COF-X wt % Rh (b-e) containing varying amounts of Rh from 2.74 to 11.38 wt %. In contrast to the known Rh catalysts, TPB-DMTP-COF-X wt % Rh (b-e) display an uncommon synergistic effect and exceptional steric confinement effect of nanochannels. Therefore, they possess the advantages of both homogeneous catalysts in high activity and selectivity and heterogeneous catalysts in stability and recyclability with extremely high activity up to 1.3 × 10⁷ g·mol_Rh^-1·h^-1 and cis-selectivity up to 99% and can be readily recycled and reused five times in the polymerization of phenylacetylene and its derivatives, affording cis-transoidal polyphenylacetylene and its derivatives having helical structures, aggregation-induced emission properties, or fluorescence properties with narrow molecular weight distributions.

Keywords: alkyne; covalent organic framework; heterogeneous catalysis; polymerization; supported catalysts.