Thiazolo[5,4‐d]Thiazole‐Linked Conjugated Porous Organic Polymers for Visible Light‐Driven C‐N Bond Formation Reactions

IF 3.8 3区化学 Q2 CHEMISTRY, PHYSICAL

ChemCatChem Pub Date : 2024-08-29 DOI:10.1002/cctc.202401327

Yuan-Yuan He, Zhang-Peng Ma, Chun-Hua Liu, Yuan-Yuan Zhu

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引用次数: 0

Abstract

Due to their unique semiconducting properties, conjugated porous organic polymers (CPOPs) have garnered significant interest in various photocatalysis applications. In this study, we synthesize three thiazolo[5,4‐d]thiazole (TzTz)‐linked CPOPs with three polyaryl rigid cores of benzene (CPOP1), pyrene (CPOP2), and triazine (CPOP3). We investigated their efficacy in catalyzing visible light‐driven C‐N bond formation reactions, including C‐N cross‐couplings between aryl bromides and amines and amination reactions from aryl bromides and sodium azides. Among the three, only CPOP2, combined with NiCl2 or Ni(dtbbpy)Cl2, effectively facilitated these transformations. Notably, CPOP2 exhibited photocatalytic activities approximately six times higher than its small molecular counterpart C1 in both reactions. The CPOP catalyst was easily recovered through centrifugal separation and reused for five catalytic cycles with minimal loss of activity. Theoretical calculations revealed that the deliberate structural design of polyaryl moieties could effectively tune the energy gap, which is crucial for the photocatalytic activity in organic reactions. This study, therefore, demonstrates a novel application of TzTz‐linked CPOPs for heterogeneous photocatalytic organic transformations.

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用于可见光驱动的 C-N 键形成反应的噻唑并[5,4-d]噻唑连接共轭多孔有机聚合物

共轭多孔有机聚合物（CPOPs）具有独特的半导体特性，因此在各种光催化应用中备受关注。在本研究中，我们合成了三种噻唑并[5,4-d]噻唑（TzTz）连接的 CPOP，它们具有苯（CPOP1）、芘（CPOP2）和三嗪（CPOP3）三种多芳基刚性核心。我们研究了它们在催化可见光驱动的 C-N 键形成反应（包括芳基溴化物与胺的 C-N 交叉耦合反应以及芳基溴化物与叠氮化钠的胺化反应）中的功效。在这三种物质中，只有 CPOP2 与 NiCl2 或 Ni(dtbbpy)Cl2 结合使用时，才能有效促进这些转化。值得注意的是，在这两个反应中，CPOP2 的光催化活性比其小分子对应物 C1 高出约六倍。CPOP 催化剂很容易通过离心分离回收，并可重复使用五个催化循环，且活性损失极小。理论计算显示，对多芳基分子进行有意的结构设计可以有效调节能隙，而能隙对于有机反应中的光催化活性至关重要。因此，这项研究展示了 TzTz 链接的 CPOP 在异相光催化有机转化中的新应用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ChemCatChem 化学-物理化学

CiteScore

8.10

自引率

4.40%

发文量

511

审稿时长

1.3 months

期刊介绍： With an impact factor of 4.495 (2018), ChemCatChem is one of the premier journals in the field of catalysis. The journal provides primary research papers and critical secondary information on heterogeneous, homogeneous and bio- and nanocatalysis. The journal is well placed to strengthen cross-communication within between these communities. Its authors and readers come from academia, the chemical industry, and government laboratories across the world. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies, and is supported by the German Catalysis Society.