Symmetry breaking in Prussian Blue Analogues via growth--guided local ordering of hexacyanometallate vacancies

Abstract: We report Growth--Guided Local Ordering, a novel mechanism of symmetry reduction in disordered crystals. This mechanism operates through the directional ordering of point defects during crystal growth, where defect correlations develop preferentially along the growth direction, resulting in reduced symmetry that persists in the final structure through the spatial distribution of defects. We demonstrate this phenomenon in Mn[Co]-Prussian Blue Analogues, disordered cyanide crystals containing numerous Co(CN)$_6$ vacancies. Single crystal diffuse scattering reveals pronounced anisotropy in vacancy distribution: strong correlations along [001] growth direction contrast with weak correlations perpendicular to it. This local ordering reduces the Laue symmetry to tetragonal $4/mmm$, evident in properties such as birefringence, while the average structure retains cubic $m\bar 3m$ symmetry. When growth proceeds along [111] direction, the same mechanism produces domains with trigonal symmetry. Because this mechanism relies on fundamental aspects of crystal growth rather than specific material properties, it offers a general strategy for symmetry control in disordered crystals. Crucially, it transforms the complex task of altering crystal symmetry into the more manageable challenge of controlling growth direction, achievable through various established techniques such as the use of surfactants during crystallization.