Substrate Stabilized Charge Transfer Scheme In Coverage Controlled 2D Metal Organic Frameworks

Abstract Recently, 2D metal‐organic frameworks (2D MOFs), characterized by complex charge transfer mechanisms, have emerged as a promising class of networks in the development of advanced materials with tailored electronic and magnetic properties. Following the successful synthesis of a 2D MOF formed by nickel (Ni) linkers and 7,7,8,8‐tetracyanoquinodimethane (TCNQ) ligands, this work investigates how the Ni‐to‐ligand ratio influences the electronic charge redistribution in an Ag(100)‐supported 2D MOF. The interplay between linker‐ligand and substrate‐MOF charge transfer processes leads to a stable equilibrium, resulting in a robust electronic structure that remains independent of stoichiometric ratios. This stability is primarily based on the electron transfer from the metal substrate, which compensates for charge imbalances introduced by the metal‐organic coordination across different MOF configurations. Despite minor changes observed in the magnetic response of the Ni centers, these findings emphasize the robustness of the electronic structure, which remains largely unaffected by structural variations, highlighting the potential of these 2D MOFs for advanced applications in electronics and spintronics.