Highly Specific Coordination-Driven Self-Assembly of 2D Heterometallic Metal–Organic Frameworks with Unprecedented Johnson-type (<i>J</i><sub>51</sub>) Nonanuclear Zr-Oxocarboxylate Clusters
Wei Gong, Hadi D. Arman, Zhijie Chen, Yi Xie, Florencia A. Son, Hui Cui, Xinfa Chen, Yanshu Shi, Yan Liu, Banglin Chen, Omar K. Farha, Yong Cui
Abstract
The quest for new and unique polynuclear metal-oxocarboxylate clusters has led to a continual boom of highly connected and robust metal–organic frameworks (MOFs) with intriguing properties. In this work, by virtue of a highly specific coordination-driven cluster rearrangement process of a presynthesized trinuclear zirconocene-based tripodal metallo-pyridine ligand, we realized the preparation of the first two 2D heterometallic MOFs incorporating unprecedented Johnson-type (J51) nonanuclear Zr-oxocarboxylate clusters, as unambiguously uncovered by single-crystal X-ray crystallography. The resultant two charged frameworks feature counteranion-dependent 3,6-c kgd (JMOF-1) and 3,12-c 3,12L4 (JMOF-2) nets that are formed by octahedral and hexagonal prismatic Zr9 molecular building blocks (MBBs), respectively. In addition, JMOF-2 shows promise for the purification of acetylene from CO2 and C2H4, with IAST selectivities of about 12 and 8, respectively, at 298 K and 1 bar, as well as remarkable iodine capture capacity of up to 2.4 g g–1.