Mixed metal node effect in zeolitic imidazolate frameworks

We synthesized two series of bimetallic (zinc and cobalt) zeolitic imidazolate frameworks (ZIF-62) under different solvothermal conditions. It is found that the structure of the derived ZIF crystals is highly sensitive to synthesis conditions. One series possesses the standard ZIF-62 structure, whereas the other has a mixed structure composed of both the standard structure and an unknown one. The standard series exhibits a slight negative deviation from linearity of melting temperature (T-m) and glass transition temperature (T-g) with the substitution of Co for Zn. In contrast, the new series displays a stronger negative deviation. These negative deviations from linearity indicate the mixed metal node effect in bimetallic ZIF-62 due to the structural mismatch between Co2+ and Zn2+ and to the difference in their electronic configurations. The new series involves both cobalt-rich and zinc-rich phases, whereas the standard one shows one homogeneous phase. Density functional theory calculations predict that the substitution of Co for Zn increases the bulk modulus of the ZIF crystals. This work indicates that the structure, melting behaviour, and mechanical properties of ZIFs can be tuned by metal node substitution and by varying the synthetic conditions. Both series of ZIFs have higher glass forming abilities due to their higher T-g/T-m ratios (0.77-0.84) compared to most good glass formers.

Automated summary

In this study, two series of bimetallic ZIF-62 were synthesized under different solvothermal conditions. The structure of the derived ZIF crystals was found to be highly sensitive to synthesis conditions. The substitution of Co for Zn led to a negative deviation from linearity in terms of melting temperature (T-m) and glass transition temperature (T-g). The new series showed a stronger negative deviation due to the mixed metal node effect. Both series exhibited different phases, with the new series having cobalt-rich and zinc-rich phases while the standard one only had a homogeneous phase. The study also demonstrated that the structure, melting behavior, and mechanical properties of ZIFs can be tuned by metal node substitution and synthetic conditions.