This thesis presents an alternative explanation for the melting mechanism of Metal-Organic Frameworks (MOFs), a relatively young class of materials that exhibits different structural behaviour from other materials. 

The interest in the melting mechanism stems from a combination of practical applications, such as the potential of glass forming the material for use in specific cases, and for a theoretical understanding of why the melting behaviour of these materials is different.

The thesis consists of a detailed state-of-the-art that explores the intricate details of MOF structural behavior. It also includes three research papers examining unique thermally activated behaviors in MOFs:

• The first paper investigates the structural and thermodynamic behavior of MOFs. Exothermic transitions in materials are linked to recrystallization events. However, in MOFs, exothermic transitions do not always result in recrystallization. The reason and mechanism behind these unique exothermic events in MOFs are explored and discussed.
• The second paper examines the unique thermal expansion behavior of MOFs. A difference between pressure-related and thermal expansion is revealed, and its connection to melting behavior is discussed.
• The third paper explores the relationship between chemical breakdown and melting in MOFs, as the former often prevents the latter. The importance of structural stability in regard to chemical stability is highlighted and reveals that what is considered a simple chemical breakdown is an intricate interplay between structure and chemistry.

Overall, the thesis argues that the general melting models do not adequately explain the behavior of MOFs. Structural compatibility with an amorphous phase has to be considered first. Then, the chemical stability of the liquid phase has to be evaluated. If both apply, steric effects influence the melting temperature of the MOF