Functionalization of MOF pore walls with azine groups enables greater interaction between the walls and substrate molecules, thereby increasing catalytic activity of the MOFs.

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Micro-and nanorods and plates of three porous Zn(II)-based metal−organic frameworks, [Zn 2 (oba) 2 (4-bpdb)] n •2(DMF) (TMU-4), [Zn(oba)(4-bpdh) 0.5 ] n •1.5(DMF) (TMU-5), and [Zn(oba)(4-bpmb) 0.5 ] n 1.5(DMF) (TMU-6) were synthesized by the coordination modulation method. The effects of concentration of modulator, temperature, and time of reaction on size and morphology have been investigated. Also, catalytic performance of TMU-5 nanosized metal−organic framework in Knoevenagel condensation reaction was evaluated.

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The amine group of the 2-amino-1,4-benzenedicarboxylic acid (NH 2 -BDC) ligand in a novel two-fold interpenetrated metal-organic framework, ijZnIJNH 2 -BDC)IJ4-bpdb)]Ĵ2DMF IJTMU-17-NH 2 ) has been found to be a base catalyst active site. TMU-17-NH 2 consists of both NH 2 -BDC and the N,N′-bipyridine-type rigid linkers (4-bpdb = 1,4-bisIJ4-pyridyl)-2,3-diaza-2,3-butadiene) with ZnN 2 O 4 secondary building units (SBUs). The MOF was characterized by FT-IR spectroscopy, elemental analysis, powder X-ray diffraction, thermal gravimetric analysis and single-crystal X-ray diffraction. The amine-functionalized framework was used as an efficient heterogeneous base catalyst for the synthesis of tetrahydro-chromenes. Excellent conversions were obtained under mild conditions in the presence of 6 mol% catalyst. The TMU-17-NH 2 catalyst could be reused several times without significant degradation in catalytic activity.