Reentrant Spin Glass and Large Coercive Field Observed in a Spin Integer Dimerized Honeycomb Lattice

2D magnetic materials with dimerized honeycomb lattices can be treated as mixed-spin square lattices, in which a quantum phase transition may occur to realize the Bose–Einstein condensation of magnons under reachable experimental conditions. However, this has never been successfully realized with integer spin centers. Herein, a spin integer (S = 2) dimerized honeycomb lattice in an iron(II)-azido compound [Fe(4-etpy)₂(N₃)₂]_n (FEN, 4-etpy = 4-ethylpyridine) is realized. Morphology characterization by transmission electron microscopy, scanning electron microscopy, and atomic force microscopy spectroscopies show that the thinnest place of the sample is ≈13 nm, which is equal to ten layers of the compound. In contrast to the common magnetic properties of long-range magnetic ordering, Mössbauer and polarized neutron scattering studies reveal that FEN exhibits a reentrant spin glass behavior owing to competing ferro- and antiferromagnetic exchange-coupling interactions within the lattice. Two spin glass phases with disparate canting angles are characterized at 39 and 28 K, respectively. By using Curély's model, two exchange-coupling constants (J₁ = +35.8 cm⁻¹ and J₂ = −3.7 cm⁻¹) can be simulated. Moreover, a very large coercive field of ≈1.9 Tesla is observed at 2 K, making FEN a “very hard” van der Waals 2D magnetic material.