近日，三峡大学王龙团队报道了偶联催化剂平面化和共轭微孔聚合物扩环增强内建电场促进C(sp³)-H磷酸化中的电荷迁移。该项研究成果发表在2025年12月29日出版的《中国化学》杂志上。

在电荷转移过程中最小化能量耗散是构建高效光催化剂的关键。然而，结构单元固有的空间位阻不可避免地引发光催化剂框架的扭转畸变，从而阻碍有效的电荷迁移。

为解决这一问题，研究组提出通过催化剂环扩张策略以提升催化性能。他们以[2,2']-联噻吩-5,5'-二甲醛（给体）与甲酰基位置异构体（1,3-或1,4-二乙酰苯连接单元）合成了共轭微孔聚合物。结构表征表明，与采用1,3-连接单元的m-SSCMP相比，基于1,4-连接单元构建的p-SSCMP展现出扩张的环状结构、增多的分子内给体-受体构型以及减小的苯基-吡啶二面角。这些结构优化显著提升了电荷迁移效率。最终，优化后的催化剂实现了高效的C(sp³)-H膦酰化反应，为光电材料与生物活性分子中引入磷酰基团提供了可持续策略。尤为重要的是，该研究建立了单体结构与催化剂电荷迁移效率之间的构效关系，为聚合物光催化剂设计提供了分子层面的理论依据。

附：英文原文

Title: Coupling Catalyst Planarization and Built-in Electric Fields Enhancement by Ringexpansion of Conjugated Microporous Polymers for Boosting Charge Migration in C(sp3)-H Phosphorylation

Author: Tianyu Long, Tao Gao, Guobin Chen, Han-Han Kong, Qing-Qing Yang, Wenli Xu, Shangbin Xiao, Liqun Ye, Long Wang

Issue&Volume: 2025-12-29

Abstract: Minimizing energy dissipation during charge transfer is essential for constructing efficient photocatalysts. However, the inherent steric constraints within building blocks inevitably induce torsional distortions in the photocatalyst framework, thereby impeding efficient charge migration. To address this, catalyst ring expansion was proposed to enhance catalytic performance. Conjugated microporous polymers (CMPs) were synthesized using [2,2']-bithiophene-5,5'-dicarbaldehyde (donor) and formyl positional isomers (1,3- or 1,4-diacetylbenzene linkers). Structural characterization revealed that compared to m-SSCMP (1,3-linker), p-SSCMP constructed with the 1,4-linker exhibits an expanded cyclic architecture, increased intramolecular D-A configurations and a reduced phenyl-pyridine dihedral angle. These structural modifications significantly accelerated charge migration efficiency. As a result, the optimized catalysts facilitated efficient C(sp3)-H phosphorylation reactions, offering a sustainable strategy for introducing phosphoryl groups into optoelectronic materials and bioactive molecules. Importantly, correlation between monomer structure and catalyst charge migration efficiency was established, providing molecular-level insights for the design of polymeric photocatalysts.

DOI: 10.1002/cjoc.70430

Source: https://onlinelibrary.wiley.com/doi/10.1002/cjoc.70430