Function–Structure Relationship in Metal–Organic Frameworks for Mild, Green, and Fast Catalytic C–C Bond Formation

Tunability in chemical functionality is a promising characteristic of metal–organic frameworks (MOFs), which plays an important role in developing and improving the practical applications of MOFs. Here, we applied this important feature of MOFs to be in line with sustainable development and green chemistry principles through the synthesis of MOF-based heterogeneous organocatalysts. According to our green functionalization strategy, some isostructural MOFs (azine decorated TMU-4 with the formula [Zn­(OBA)­(BPDB)_0.5]_n·2DMF, azine-methyl functionalized TMU-5 with the formula [Zn­(OBA)­(BPDH)_0.5]_n·1.5DMF, dihydro-tetrazine decorated TMU-34 with the formula [Zn­(OBA)­(H₂DPT)_0.5]_n·DMF, and tetrazine functionalized TMU-34­(−2H) with the formula [Zn­(OBA)­(DPT)_0.5]_n·DMF, where H₂OBA = 4,4′-oxybis­(benzoic acid), BPDB = 1,4-bis­(4-pyridyl)-2,3-diaza-1,3-butadiene, BPDH = 2,5-bis­(4-pyridyl)-3,4-diaza-2,4-hexadiene, H₂DPT = 3,6-di­(pyridin-4-yl)-1,4-dihydro-1,2,4,5-tetrazine, and DPT = 3,6-di­(pyridin-4-yl)-1,2,4,5-tetrazine) have been applied for mild, green, and fast Knoevenagel condensation. These frameworks display different Lewis basic catalytic activities owing to their different functionality and function accessibility. Contrary to extensive articles published about Knoevenagel condensation, this study involves the rare examples in Knoevenagel condensation with such mild conditions (room temperature and atmospheric pressure) and with a green solution (water as the solvent). Due to the combined synergic effects of the Lewis basicity of TMU-frameworks, the amphoteric and hydrogen bond-participating nature of water molecules, maximum conversion times are reached just after 30 min (for TMU-5) and 60 min (for TMU-34). Stability and recyclability tests show that TMU-5 and TMU-34 are completely stable in water at reaction conditions and can retain their crystallinity, porosity, and functionality even after five cycles without any specific reduction in their catalytic conversion. Since, in many cases, amine decorated MOFs are applied in Knoevenagel catalyzed condensation, this study is beneficial in providing information about the effects of azine and tetrazine functional groups in reactant activation and the acceleration of Knoevenagel condensation.