Leveraging Isothermal Titration Calorimetry to Obtain Thermodynamic Insights into the Binding Behavior and Formation of Metal-Organic Frameworks

Isothermal titration calorimetry (ITC) is a techniquewhich directly measures the thermodynamic parameters of binding events.Although historically it has been used to investigate interactions inbiological macromolecules and the kinetics of enzyme-catalyzed reactions,ITC has also been demonstrated to provide relevant thermodynamicinformation about interactions in synthetic systems, such as those inmetal-organic frameworks (MOFs). MOFs are a family of crystallineporous materials that have been widely studied as supports for moleculesranging from gases to biomolecules through physisorption andchemisorption. Herein, we offer a perspective on the current applicationsof ITC in MOFs, including the mechanism of small molecule adsorptionand the formation of MOF-based composite materials through non-covalent interactions. Experimental considerations specific to running ITCexperiments in MOF systems are reviewed on the basis of existing reports. We conclude by discussing underexplored, but promising,MOF-related research directions which could be elucidated by ITC.