High‐Throughput Discovery of a Rhombohedral Twelve‐Connected Zirconium‐Based Metal‐Organic Framework with Ordered Terephthalate and Fumarate Linkers. Issue 52 (16th November 2021)

• Record Type: Journal Article
• Authors: Tollitt, Adam M.; Vismara, Rebecca; Daniels, Luke M.; Antypov, Dmytro; Gaultois, Michael W.; Katsoulidis, Alexandros P.; Rosseinsky, Matthew J.
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 52(2021)
• Page Start: 26939
• Page End: 26946
• Publication Date: 2021-11-16
• Subjects: chemical space -- high-throughput synthesis -- Metal-organic frameworks -- ordered linkers -- rhombohedral distortion; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202108150
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: We report a metal‐organic framework where an ordered array of two linkers with differing length and geometry connect [Zr6 (OH)4 O4 ] 12+ clusters into a twelve‐connected fcu net that is rhombohedrally distorted from cubic symmetry. The ordered binding of equal numbers of terephthalate and fumarate ditopic carboxylate linkers at the trigonal antiprismatic Zr6 core creates close‐packed layers of fumarate‐connected clusters that are connected along the single remaining threefold axis by terephthalates. This well‐defined linker arrangement retains the three‐dimensional porosity of the Zr cluster‐based UiO family while creating two distinct windows within the channels that define two distinct guest diffusion paths. The ordered material is accessed by a restricted combination of composition and process parameters that were identified by high‐throughput synthesis. Abstract : The ordered arrangement of terephthalate and fumarate linkers over the fcu net produces a zirconium‐based MOF Zr6 (BDC)3 (Fum)3 with two distinct windows and multiple guest diffusion pathways. This phase is formed by single‐step synthesis in a narrow region of the available chemical space, and its identification required a large set of synthetic experiments that were facilitated by automated high‐throughput methods.