The two-dimensional metal–organic
framework (2D
MOF) has
potential applications in spintronics and catalytics due to the tunable
structure, high crystallinity, and porosity. However, the study of
the physical properties of a precise single-crystal 2D MOF is rare
because of the small crystals or poor quality, which hinders the practical
application. In this work, based on the successful fabrication of
200 μm single-crystal 2D Cu3(HHTT)2 and
Ni3(HHTT)2 (HHTT = 2,3,7,8,12,13-hexahydroxy
tetraazanaphthotetraphene), the electronic, magnetic, and catalytic
properties of 2D M3(HHTT)2 (M = 3d transition
metals) were studied by first-principles calculations. Cr3(HHTT)2 and Cu3(HHTT)2 exhibit out-of-plane
ferromagnetic spin-gapless semiconductor properties with opposite
spin polarization. When the spin-orbit coupling is considered, Cr3(HHTT)2 opens a gap of 3.37 meV around the Fermi
level and shows a quantum anomalous Hall effect with the Chern number C = 1. Cr3(HHTT)2 shows a lower overpotential
(0.66 eV) than that of Cu3(HHTT)2 (1.94 eV)
for electrocatalytic CO2 reduction reactions. Additionally,
Mn3(HHTT)2 exhibits robust out-of-plane ferrimagnetic
semiconducting properties. M3(HHTT)2 (M = Ti,
Fe, and Co) and V3(HHTT)2 exhibit in-plane spin-gapless
semiconductor properties with an opposite spin polarization. These
results provide candidates for the study of spintronics and electrocatalysts.