Postsynthetic Oxidation of the Coordination Site in a Heterometallic Metal-Organic Framework: Tuning Catalytic Behaviors

Journal Article · Tue Jun 23 00:00:00 EDT 2020 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.0c01267· OSTI ID:1646834

Han, Yi ^[1]; Sinnwell, Michael A.  ^[2]; Surbella, Robert G.  ^[2]; Xue, Wenjuan ^[3]; Huang, Hongliang ^[3]; Zheng, Jian  ^[2]; Peng, Bo ^[2]; Verma, Gaurav ^[4]; Yang, Yang  ^[2]; Liu, Lili  ^[2]; Ma, Shengqian ^[4]; Thallapally, Praveen K.  ^[2]

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1. Qingdao University of Science and Technology
2. BATTELLE (PACIFIC NW LAB)
3. Tianjin Polytechnic University
4. University of South Florida

Postsynthetic modification (PSM) in metal-organic frameworks (MOFs) can introduce multiple functionalities and alter the structural function for the desired application. However, the PSM of the coordination site faces the challenges of structural collapse or incompatibility between the original metal site and the newly formed coordination group. Herein, we developed a novel concept of introducing “primary” and “secondary” nodes, coexisting in a water-stable, Zr-based heterometallic MOF, [Zr6(µ3-OH)8(OH)8][CuI4(L1)4]2 (1-SH-a, H2L1 = 6-mercaptopyridine-3-carboxylic acid). The post-synthetic oxidation at the coordination site was successfully achieved in the “secondary” nodes [CuI4(L1)4]4-, while the robust “primary” nodes [Zr6(µ3-OH)8(OH)8]8+ stabilized the whole framework to form [Zr6(µ3-OH)8(OH)8][(CuI0.44CuII0.56(OH)0.56)4(L2)4]2 (1-SO3H, H2L2 = 6-sulfonicotinic acid). PSM of 1-SH-a to form 1-SO3H dramatically tuned the catalytic properties toward the styrene oxide ring-opening reaction to give a regioselectivity of primary alcohol (A) of ~99% compared with 1-SH-a (~71%).

• Research Organization: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1646834
• Report Number(s): PNNL-SA-148450
• Journal Information: Chemistry of Materials, Vol. 32, Issue 12
• Country of Publication: United States
• Language: English