How to Get Away With Instability: Understanding Degradation Mechanisms in Unstable Metal–Organic Frameworks

ABSTRACT Metal–organic frameworks (MOFs) represent a versatile class of crystalline porous materials utilized in gas storage, catalysis, and separations. While their modularity allows for exceptional tunability, practical implementation is frequently hindered by structural instability. Many frameworks undergo degradation when exposed to moisture, heat, mechanical stress, or reactive chemicals. This review provides a comprehensive analysis of the degradation mechanisms governing MOF instability, exploring primary pathways including chemical, thermal, mechanical, and photochemical degradation. The influence of environmental factors such as humidity, solvent polarity, pH, and operational cycling is detailed alongside strategies to counteract these vulnerabilities. Specifically, we discuss stabilization techniques involving post‐synthetic modification, the formation of robust composite and hybrid materials, and the critical role of controlled synthesis parameters. A central thesis emerges: instability is not merely a flaw to be eradicated but a complementary aspect of MOF behavior that can be controlled and harnessed. We highlight opportunities for designed instability, where controlled defect engineering and dynamic framework responses are engineered into materials. This perspective shifts the focus from static permanence to dynamic resilience, enabling the design of adaptive, self‐regulating frameworks for advanced applications.