Sensitivity of the glass transition and melting in a metal-organic framework to ligand chemistry.

The effect of substituting linkers with electron-donating moieties for part of the conventional ones on the melting and glass transition behaviours of ZIF-62 was investigated by calorimetry and X-ray diffraction. Specifically, substituting 5,6-dimethylbenzimidazole for benzimidazole in ZIF-62 increases both T m and T g . The structural origin of this effect was explained.