The binding energy of an electron in a material is a fundamental
characteristic, which determines a wealth of important chemical and physical
properties. For metal-organic frameworks this quantity is hitherto unknown. We
present a general approach for determining the vacuum level of porous
metal-organic frameworks and apply it to obtain the first ionisation energy for
six prototype materials including zeolitic, covalent and ionic frameworks. This
approach for valence band alignment can explain observations relating to the
electrochemical, optical and electrical properties of porous frameworks
