Lauren E. Hatcher

The switching behavior of the novel hybrid material (FA)Na[Fe(CN) 5 (NO)].H 2 O ( 1 ) in response to temperature ( T ), light irradiation and electric field ( E ) is studied using in situ X‐ray diffraction (XRD). Crystals of 1 display piezoelectricity, pyroelectricity, second and third harmonic generation. XRD shows that the FA + are disordered at room‐temperature, but stepwise cooling from 273–100 K induces gradual ordering, while cooling under an applied field ( E =+40 kVcm −1 ) induces a sudden phase change at 140 K. Structural‐dynamics calculations suggest the field pushes the system into a region of the structural potential‐energy surface that is otherwise inaccessible, demonstrating that application of T and E offers an effective route to manipulating the crystal chemistry of these materials. Photocrystallography also reveals photoinduced linkage isomerism, which coexists with but is not correlated to other switching behaviors. These experiments highlight a new approach to in situ studies of hybrid materials, providing insight into the structure–property relationships that underpin their functionality.