Band Alignment as the Method for Modifying Electronic Structure of Metal-Organic Frameworks

Electronic-level ordering in metal-organic frameworks (MOFs) is a route to modulate their electronic properties such as optical absorption, band alignment, work function, charge separation, charge carrier lifetimes, and ground- or excited-state conductivity. A systematic application of this approach requires the knowledge on how a MOF chemical composition affects its electronic structure. In this work, the fundamental principles for selecting MOF components to achieve targeted level alignment are considered. Correlations between the electronic parameters of building blocks and MOF band structure are analyzed. The factors affecting the energy position of constituents are discussed. In particular, the impact of the chemical composition of ligands, including the structure of its scaffold and side groups, on their energy positions in MOFs is addressed. Besides, the effect of the choice of reference potential and surface termination on the band alignment is investigated. The performance of several density functionals in the computation of absolute band positions is assessed. Finally, general principles for the modification of the MOF electronic structure are formulated and the routes to achieve an appropriate band alignment with carrier-transporting materials, co-catalysts, and redox reaction potentials are suggested.