近日，山东理工大学邢令宝团队报道了电子转移介体赋能的模块化控制卟啉超分子框架中单线态氧（¹O₂）和超氧阴离子自由基（O₂^•–）的产生，用于选择性光合作用。2026年1月27日出版的《德国应用化学》杂志发表了这项成果。

经典II型光敏剂通过能量转移产生单线态氧的固有倾向，是开发能够通过电子转移产生活性氧自由基的I型体系面临的关键挑战。

研究组报道了一种基于卟啉的超分子有机框架，该框架通过与葫芦脲的主客体相互作用组装而成，其单线态氧量子产率显著提升至94.04%，远高于单体单元TPP-BPY的74.52%。为克服能量转移主导的活性氧生成途径，研究引入了一系列电子转移介质来调控激发态动力学，最终获得的BQ@TPP-BPY-CB[8]体系成功将活性氧生成路径从II型切换为I型。这种介质驱动的调控策略不仅能在低氧条件下实现超氧自由基的生成，还拓展了超分子框架体系的功能多样性。

两种活性氧生成路径在光催化应用中展现出选择性优势：TPP-BPY-CB[8]在单线态氧介导的有机磷化合物氧化反应中表现优异，而BQ@TPP-BPY-CB[8]则通过促进超氧自由基生成实现了高效的硫醇-烯点击交联反应。该研究为超分子光催化体系中活性氧生成的定向调控提供了有效策略，为开发多功能、活性氧定向的光反应材料提供了新的设计范式。

附：英文原文

Title: Electron Transfer Mediator–Enabled Modular Control of 1O2 and O2•– Generation in Porphyrin Supramolecular Frameworks for Selective Photosynthesis

Author: Wen-Qiang Liu, Fa-Dong Wang, Hui Liu, Ling-Bao Xing

Issue&Volume: 2026-01-27

Abstract: The inherent preference of classical type II photosensitizers for generating singlet oxygen (1O2) via energy transfer presents a key challenge in developing type I systems capable of producing superoxide radicals (O2–) through electron transfer. Herein, we report a porphyrin-based supramolecular organic framework (SOF, TPP-BPY-CB[8]) assembled via host–guest interactions with cucurbit[8]uril (CB[8]), which achieves a significantly enhanced 1O2 quantum yield (94.04%) compared to the monomeric unit TPP-BPY (74.52%). To overcome the energy transfer-dominated reactive oxygen species (ROS) pathway, a series of electron transfer mediators were introduced to modulate the excited-state dynamics, resulting in BQ@TPP-BPY-CB[8] that effectively switches the ROS pathway from type II to type I. This mediator-driven modulation not only enables O2– production under hypoxic conditions but also expands the functional diversity of the SOF system. The two ROS pathways are selectively leveraged in photocatalytic applications: TPP-BPY-CB[8] excels in 1O2-mediated oxidation of organophosphorus compounds, while BQ@TPP-BPY-CB[8] facilitates highly efficient thiol-ene cross-coupling via O2– promotion. This work presents a robust strategy for tailoring ROS generation in supramolecular photocatalysis, offering a new design paradigm for multifunctional, ROS-directed photoreactive materials.

DOI: 10.1002/anie.202519699

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202519699