Ma Zhen-Sha, Zhang Jian, Zhou Kang, Lu Gonghao, Liu Xiao-Yuan
Hoffmann Institute of Advanced Materials, Shenzhen Polytechnic University, 7098 Liuxian Blvd, Nanshan District, Shenzhen 518055, P. R. China.
School of Chemical Engineering, University of Science and Technology Liaoning, 185 Qianshan Zhong Road, Anshan 114051, P. R. China.
Inorg Chem. 2025 Jan 27;64(3):1604-1610. doi: 10.1021/acs.inorgchem.4c05128. Epub 2025 Jan 11.
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 Zr cluster to 8- and 9-connected and to 9- and 12-connected Zr 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.
在过去三十年中，金属有机框架得到了广泛的发展，它们通常是通过无机建筑单元与市售或预合成的有机连接体之间的反应构建而成。然而，由于多步分离和纯化，有机连接体的预合成通常既耗时又不可持续。因此，开发一种新策略的方法对于金属有机框架的构建和进一步探索其应用至关重要。在此，我们报道了一种受德布斯-拉迪谢夫斯基反应启发的原位“一锅法”策略，其中从三种简单且市售的前体生成有机连接体以及金属有机框架的顺序构建被整合到一个溶剂热条件中。基于此方法，成功制备了两种锆四羧酸盐框架（HIAM-4028-op和HIAM-4029-op），它们分别表现出亮蓝色和近红外发射。由于HIAM-4028-op的配位不饱和金属位点和低对称性，单晶中的配位模式可以通过二级连接体的安装从原始的8连接Zr簇转移到8连接和9连接以及9连接和12连接Zr簇共存的结构。据我们所知，目前的工作是首次使用受德布斯-拉迪谢夫斯基反应启发的原位“一锅法”策略构建金属有机框架，这为设计和构建具有特定性质和结构的金属有机框架开辟了一条新途径。
