Band Structure Engineering in 2D Metal–Organic Frameworks

Abstract

Abstract The design of 2D metal–organic frameworks (2D MOFs) takes advantage of the combination of the diverse electronic properties of simple organic ligands with different transition metal (TM) centers. The strong directional nature of the coordinative bonds is the basis for the structural stability and the periodic arrangement of the TM cores in these architectures. Here, direct and clear evidence that 2D MOFs exhibit intriguing energy‐dispersive electronic bands with a hybrid character and distinct magnetic properties in the metal cores, resulting from the interactions between the TM electronic levels and the organic ligand π‐molecular orbitals, is reported. Importantly, a method to effectively tune both the electronic structure of 2D MOFs and the magnetic properties of the metal cores by exploiting the electronic structure of distinct TMs is presented. Consequently, the ionization potential characteristic of selected TMs, particularly the relative energy position and symmetry of the 3d states, can be used to strategically engineer bands within specific metal–organic frameworks. These findings not only provide a rationale for band structure engineering in 2D MOFs but also offer promising opportunities for advanced material design.

Keywords

• angle‐resolved photoelectron spectroscopy
• band structure engineering
• density functional theory
• molecular ligand
• single‐layer metal–organic framework
• transition metal