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

Abstract

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.