Abstract
Dynamic crystals with directional deformations in response to external stimuli through molecular reconfiguration, are observed predominantly in certain organic crystals and metal complexes. Low-dimensional hybrid halides, resemble these materials due to the presence of strong hydrogen bonds between bulky organic moieties and inorganic units, whereas their dynamic behavior remains largely unexplored. Here we show that a one-dimensional hybrid halide (MV)BiBr(5) (MV = methylviologen) undergoes an isosymmetric phase transition at hydrostatic pressure of 0.20 GPa, accompanied by a remarkable length expansion of 20-30% and red to dark yellow color change. Unexpectedly, the backward transition can be fully reversed by mechanical stimulation rather than decompression. In the high-pressure phase, the coexistence of strong Bi(3+) lone pair stereochemical activity and large reorientations of the planar MV(2+) cations, together with the newly formed CH···Br hydrogen interactions, are the structural features that facilitate microscopic changes and stabilize the metastable high-pressure phase at ambient conditions.