Debus-Radziszewski Reaction Inspired In Situ "One-Pot" Approach to Construct Luminescent Zirconium-Organic Frameworks

作     者：Ma, Zhen-Sha Zhang, Jian Zhou, Kang Lu, Gonghao Liu, Xiao-Yuan 

作者机构：Shenzhen Polytech Univ Hoffmann Inst Adv Mat Shenzhen 518055 Peoples R China Univ Sci & Technol Liaoning Sch Chem Engn Anshan 114051 Peoples R China 

出 版 物：《INORGANIC CHEMISTRY》 (Inorg. Chem.)

年 卷 期：2025年第64卷第3期

页      面：1604-1610页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 070301[理学-无机化学] 

基　　金：Shenzhen Polytechnic Shenzhen Polytechnic University Shenzhen Science and Technology Program Shenzhen Science and Technology Innovation Commission [6022312041K] Research Foundation of Shenzhen Polytechnic University Research 

主　　题：Carboxylation 

摘      要：Metal-organic frameworks have received extensive development in the past three decades, which are generally constructed via the reaction between inorganic building units and commercially available or presynthesized organic linkers. However, the presynthesis of organic linkers is usually time-consuming and unsustainable due to multiple-step separation and purification. Therefore, methodology development of a new strategy is fundamentally important for the construction and further exploration of the applications of MOFs. Herein, we report an in situ one-pot strategy inspired by the Debus-Radziszewski reaction, in which the generation of organic linkers from three kinds of simple and commercially available precursors and sequential construction of MOFs are integrated into one solvothermal condition. Based on this method, two zirconium-tetracarboxylate frameworks (HIAM-4028-op and HIAM-4029-op) were successfully prepared, which exhibit bright blue and near-infrared emissions, respectively. Due to the coordinatively unsaturated metal sites and the low symmetry of HIAM-4028-op, the coordination modes in the single crystal can transfer from the pristine 8-connected Zr6 cluster to 8- and 9-connected and to 9- and 12-connected Zr6 cluster coexisting structures via secondary linker installation. To the best of our knowledge, the present work is the first time to construct MOFs using a Debus-Radziszewski reaction-inspired in situ one-pot strategy, which opens a new way to design and construct MOFs with specific properties and structures.