Metallaphotocatalytic Amination of Aryl Chlorides Enabled by Highly Crystalline Acetylene-Based Hydrazone-linked Covalent Organic Frameworks

30 March 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Amination of aryl chlorides by metallaphotocatalysis is highly desired but remained practically challenging. Meanwhile, relying on soluble noble-metal photocatalysts suffers from resource scarcity and structural instability which limit their practical application. Here in, a highly crystalline acetylene-based hydrazone-linked BTH-THFEB COF is reported that enable metallaphotocatalytic amination of aryl chlorides. The non-planar effect of hydrazone linkage and weak interlayer attraction of acetylene bond were minimized by intralayer hydrogen-bonding. As a result, the COF showed not only an improved crystallinity and porosity, but also enhanced optical and electronic properties compared to a COF analogue without hydrogen-bonding. Notably, dual BTH-THFEB/Ni system afforded C─N coupling products from broad aryl chloride substrates in excellent yields (up to 99%) and good functional tolerance. Furthermore, BTH-THFEB is recoverable and reusable for five times photocatalysis cycles. This report demonstrates simple approach to tune the structure-activity relationship in COFs at molecular level.

Keywords

Metallaphotocatalysis
Covalent organic frameworks
Aryl chlorides
Photocatalysis
Ni catalysis

Supplementary materials

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Supporting Information
Description
Additional data on synthesis and characterization of materials as well as photocatalysis data.
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