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Postsynthetic Metal and Ligand Exchange in MFU-4l : A Screening Approach toward Functional Metal–Organic Frameworks Comprising Single-Site Active Centers

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Denysenko, D., Jelic, J., Reuter, K., & Volkmer, D. (2015). Postsynthetic Metal and Ligand Exchange in MFU-4l: A Screening Approach toward Functional Metal–Organic Frameworks Comprising Single-Site Active Centers. Chemistry – A European Journal, 21(22), 8188-8199. doi:10.1002/chem.201406564.

Cite as: https://hdl.handle.net/21.11116/0000-000A-C2DE-1
The isomorphous partial substitution of Zn2+ ions in the secondary building unit (SBU) of MFU-4l leads to frameworks with the general formula [MxZn(5–x)Cl4(BTDD)3], in which x≈2, M=MnII, FeII, CoII, NiII, or CuII, and BTDD=bis(1,2,3-triazolato-[4,5-b],[4′,5′-i])dibenzo-[1,4]-dioxin. Subsequent exchange of chloride ligands by nitrite, nitrate, triflate, azide, isocyanate, formate, acetate, or fluoride leads to a variety of MFU-4l derivatives, which have been characterized by using XRPD, EDX, IR, UV/Vis-NIR, TGA, and gas sorption measurements. Several MFU-4l derivatives show high catalytic activity in a liquid-phase oxidation of ethylbenzene to acetophenone with air under mild conditions, among which Co- and Cu derivatives with chloride side-ligands are the most active catalysts. Upon thermal treatment, several side-ligands can be transformed selectively into reactive intermediates without destroying the framework. Thus, at 300 °C, CoII-azide units in the SBU of Co-MFU-4l are converted into CoII-isocyanate under continuous CO gas flow, involving the formation of a nitrene intermediate. The reaction of CuII-fluoride units with H2 at 240 °C leads to CuI and proceeds through the heterolytic cleavage of the H2 molecule.