A Thienothiophene-Based Olefin-Linked Covalent Organic Framework for the Metal-Free Photocatalytic Oxidative Coupling of Amines

IF 5.1 Q1 POLYMER SCIENCE

ACS Macro Letters Pub Date : 2025-02-15 DOI:10.1021/acsmacrolett.4c0084710.1021/acsmacrolett.4c00847

Bertha Lotsi, Aadarsh Sharma, Jared G. Doremus, Spencer T. Burton, Claudia Turro and Psaras L. McGrier*,

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引用次数: 0

Abstract

The oxidative coupling of amines is a useful way to prepare many diverse compounds for the pharmaceutical and chemical industries. Covalent organic frameworks (COFs), a crystalline class of porous polymers, have emerged as promising heterogeneous photocatalysts that can accomplish this transformation under metal-free conditions due to their excellent photochemical stability and tunable electronic properties. Herein, we report the optoelectronic and photocatalytic properties of an olefin-linked COF containing thienothiophene (TT) and 2,4,6-trimethyl-1,3,5-triazine (TMT) units. The TT-TMT-COF exhibited a narrow band gap with extended light absorption and excellent charge separation, making it useful for the oxidative coupling of various benzylamines. The TT-TMT-COF exhibited fast reaction times, excellent recyclability, and conversions as high as ∼99%. The reactivity of TT-TMT-COF was on par or significantly better than that of a few small molecule 2,4,6-tris((E)-2-(thieno[3,2-b]thiophen-2-yl)vinyl)-1,3,5-triazine (TT-TMT) and 2,4,6-tris((E)-2-(thiophen-2-yl)vinyl)-1,3,5-triazine (Thio-TMT) homogeneous catalytic systems containing similar functional units. This work further highlights the ability of the COF to perform useful and efficient catalytic transformations in a sustainable manner.

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胺的氧化偶联是为制药和化学工业制备多种化合物的有效方法。共价有机框架（COF）是一类多孔聚合物晶体，由于其出色的光化学稳定性和可调电子特性，已成为一种很有前途的异质光催化剂，可以在无金属条件下完成这种转化。在此，我们报告了一种含有噻吩（TT）和 2,4,6-三甲基-1,3,5-三嗪（TMT）单元的烯烃连接 COF 的光电和光催化特性。TT-TMT-COF 具有窄带隙、延长的光吸收和优异的电荷分离性能，因此可用于各种苄胺的氧化偶联。TT-TMT-COF 的反应时间快，可回收性好，转化率高达 ∼ 99%。TT-TMT-COF 的反应活性与一些含有类似功能单元的小分子 2,4,6-三((E)-2-(噻吩并[3,2-b]噻吩-2-基)乙烯基)-1,3,5-三嗪（TT-TMT）和 2,4,6-三((E)-2-(噻吩-2-基)乙烯基)-1,3,5-三嗪（Thio-TMT）均相催化体系相当或明显优于它们。这项工作进一步凸显了 COF 以可持续的方式进行有用、高效催化转化的能力。

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来源期刊

ACS Macro Letters 化学-

CiteScore

10.40

自引率

3.40%

发文量

209

审稿时长

1 months

期刊介绍： ACS Macro Letters publishes research in all areas of contemporary soft matter science in which macromolecules play a key role, including nanotechnology, self-assembly, supramolecular chemistry, biomaterials, energy generation and storage, and renewable/sustainable materials. Submissions to ACS Macro Letters should justify clearly the rapid disclosure of the key elements of the study. The scope of the journal includes high-impact research of broad interest in all areas of polymer science and engineering, including cross-disciplinary research that interfaces with polymer science. With the launch of ACS Macro Letters, all Communications that were formerly published in Macromolecules and Biomacromolecules will be published as Letters in ACS Macro Letters.