A green route approach to the synthesis of Ni(II) and Zn(II) templated metal–organic frameworks

A new synthetic route involving mixing of solid reactants followed by heating has been developed for the preparation of two templated metal–organic frameworks (MOFs). [Ni(NO₃)₂(bipy)₂](pyrene)₂ (1) was obtained by mixing together Ni(NO₃)₂·6H₂O, 4,4-bipyridine and pyrene followed by heating at 85 °C for 4 h, while [Zn₂(fumarate)₂(bipy)] (2) was synthesized by mixing together Zn(O₂CCH₃)₂·2H₂O, fumaric acid and 4,4-bipyridine followed by heating at 160 °C for 16 h. The materials were characterized by elemental analysis, FT-IR spectroscopy and X-ray powder diffraction analysis (XRPD). Comparison of XRPD patterns of the materials with patterns simulated from the single crystal X-ray diffraction data, obtained from Cambridge Structural database, allowed identification of the products. Conversion of solid reactants to MOFs occurs spontaneously even when reactants are not mechanically stressed. Overall, the study suggests that MOFs can be synthesized in solid state simply by mixing together appropriate reactants without co-mill (ball-mill). Compared with traditional synthetic techniques such as solvothermal, ball-milling and solution-based, this method is environmentally friendly and highly efficient in the manufacture of these MOFs on a large scale.