近日，中国科学院福建物构所孙庆福团队提出了紫外官能化镧系有机四面体笼光开关催化发散合成。相关论文于2025年6月17日发表在《德国应用化学》杂志上。

光开关催化是一个重大挑战，特别是在反应途径的调节方面。在这项研究中，课题组描述了一种氧化还原活性镧系元素有机四面体笼1，由紫精官能化的双位三齿配体和Eu（III）离子自组装而成。与游离配体L相比，络合诱导的电荷再分配和配体在组装中的空间重排赋予1独特的光致变色性质和氧化还原活性。

1可以作为光开关催化剂，用于各种四芳基硼酸盐的发散化学转化，在365nm光照下通过光氧化偶联反应产生联芳基和酚类，或在没有光照的情况下通过催化脱组分过程生产单芳烃产品。这项工作代表了通过单个自组装配位笼进行光开关发散合成的第一个例子，为设计和构建具有可切换功能的新型超分子结构铺平了道路。

附：英文原文

Title: Photoswitchable Catalytic Divergent Synthesis by a Viologen-Functionalized Lanthanide-Organic Tetrahedral Cage

Author: Qing-Fu Sun, Ke-Han Tang, Yu-Xi Tian, Fan Yin, Wei-Hui Zhuang, Shao-Jun Hu, Li-Peng Zhou, Jian Yang

Issue&Volume: 2025-06-17

Abstract: Photoswitchable catalysis presents a significant challenge, particularly in the modulation of reaction pathways. In this study, we describe a redox-active lanthanide-organic tetrahedral cage 1, self-assembled from a viologen-functionalised ditopic tridentate ligand and Eu(III) ions. Complexation-induced charge redistribution and spatial rearrangement of ligands in the assembly endow 1 with distinct photochromic properties and redox activities compared to free ligand L. 1 can serve as a photoswitchable catalyst for divergent chemical transformations of various tetraarylborates, giving biaryls and phenols via photo-oxidative coupling reaction under 365 nm light irradiation, or producing mono-arene products through catalytic de-composition process in the absence of light. This work represents the first example of photoswitchable divergent synthesis by a single self-assembled coordination cage, paving the way for the design and construction of novel supramolecular edifices with switchable functions.

DOI: 10.1002/anie.202510095

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202510095