Spin-Electronic Properties of Two-Dimensional Metal–Organic Frameworks Based on Transition Metals: A First-Principles Study

Using first-principles calculations with the HSE06 hybrid functional, we systematically investigate the structural, electronic and magnetic properties of 2D MOFs based on four transition metals (Co, Ni, Cu, Zn) with hexaaminobenzene (HAB) linkers. All four MOFs are thermodynamically stable. Notably, they exhibit distinct magnetic ground states: Co 3 (HAB) 2 , Cu 3 (HAB) 2 and Zn 3 (HAB) 2 are ferrimagnetic, while Ni 3 (HAB) 2 is ferromagnetic. Their electronic structures also differ significantly. Co 3 (HAB) 2 is a bipolar magnetic semiconductor (BMS), Ni 3 (HAB) 2 is a half-metallic ferromagnet (HMF) with 100% spin polarization, Cu 3 (HAB) 2 is a half-semiconductor (HSC) and Zn 3 (HAB) 2 is a unipolar magnetic semiconductor (UMS). These findings demonstrate that the magnetic and electronic properties of 2D MOFs can be effectively tuned by selecting appropriate transition-metal centers.