Isosymmetric Phase Transitions in Crystals: From Subtle Rearrangements to Functional Properties

Isosymmetric phase transitions (IPTs) represent a rare class of solid-state transformations in which substantial structural reorganization occurs without a change in crystallographic symmetry. These phenomena, though subtle, can have a profound impact on the physical and functional properties of materials, offering novel opportunities for property tuning without chemical modification. This review provides a comprehensive overview of the experimental and computational methods used to detect and characterize IPTs, including single-crystal and powder X-ray diffraction, Raman and FT-IR spectroscopy, differential scanning calorimetry, and advanced simulation techniques such as density functional theory, molecular dynamics, and crystal structure prediction. Special emphasis is placed on correlating local structural rearrangements—such as hydrogen-bond reconfiguration, polyhedral tilting, and molecular fragment reorientation—with macroscopic thermodynamic signatures. A broad selection of examples from the literature is discussed, covering molecular crystals, coordination compounds, organic functional materials, simple salts, and inorganic oxides, with detailed tables summarizing pressure- and temperature-induced IPTs. The review also analyses the primary factors that trigger IPTs, particularly temperature and pressure, and examines their role in governing structural stability and transformation pathways. By combining structural, spectroscopic, and thermodynamic perspectives, this work aims to consolidate the understanding of IPT mechanisms and to highlight their significance for the design of responsive crystalline materials.