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Engineering Cooperative Microenvironments in a Nitro-Functionalized Trinuclear Copper Metal-Organic Framework for
Yanmei Li1, Kaisong Guo1, Liming Fan1
1Shanxi Key Laboratory of Hydrogen Energy Carbon Electrode Materials, School of Chemistry and Chemical Engineering, North University of China, Taiyuan 030051, P. R. China.
Abstract:
The deliberate engineering of cooperative catalytic microenvironments within metal-organic frameworks (MOFs) offers a powerful strategy for promoting sustainable catalysis. Herein, we report a robust nitro-functionalized trinuclear metal-organic framework, formulated as {[Cu3(NTCB)2(4,4'-bip)(DMF)2]·4DMF·3H2O}n (NUC-180; H3NTCB = 1,3,5-tri(4-carboxy-2-nitrophenyl)-2,4,6-trinitrobenzene, 4,4'-bip = 4,4'-bipyridine), featuring a high void fraction and dual nanoscale channel systems. Upon activation, NUC-180a exposes coordinatively unsaturated metal centers and strongly electron-withdrawing nitro functionalities that collectively regulate the local electronic environment and enhance substrate polarization. As a result, NUC-180a exhibits excellent heterogeneous catalytic performance for the solvent-free cycloaddition of CO2 with epoxides under mild conditions, delivering cyclic carbonates with high efficiency, selectivity, and recyclability. Beyond CO2 fixation, the framework also efficiently catalyzes tandem deacetalization-Knoevenagel condensation reactions. Mechanistic insights reveal that the catalytic activity originates from the synergistic interplay between Lewis-acidic metal sites and polar functional groups within the confined micropores. This work highlights nitro-functionalized MOFs as versatile platforms for cooperative catalysis without invoking classical Lewis basicity from nitro groups.
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