Reversible pressure pre-amorphization of a piezochromic metal–organic framework

Abstract

The piezochromic metal–organic framework Co₂(Bdc)₂Dabco·4DMF·H₂O (Bdc denotes 1,4-benzenedicarboxylate, Dabco – 1,4-diazabicyclo[2.2.2]octane, and DMF – dimethylformamide) under ambient conditions is tetragonal (phase α) and at about 1.9 GPa undergoes a strong pressure-induced shortening of translational correlations in the sample. A broad gradual pre-amorphization process starting at about 0.7 GPa reduces the tetragonal symmetry and is described as phase β. The pre-amorphization mechanism involves several competing distortions of the Bdc linkers and Co(II)-coordination schemes. These in turn, affect the crystal field around the cations and their optical absorption. The compression strongly affects the VIS absorption of this piezochromic compound visibly changing its colour from blue to red.