Structural, Electronic and Magnetic Properties of <scp> Cr ₂ Zn </scp> <i> _x </i> ( <i>x</i>  = 3–18) Clusters

ABSTRACT The assembly of antiferromagnetic (AFM) clusters represents a potentially effective approach to constructing AFM materials, thus driving the exploration of such clusters. Here, we investigated the structural, electronic, and magnetic properties of Cr 2 Zn x ( x = 3–18) clusters using density functional theory (DFT), revealing their antiferromagnetic coupling characteristics. The two Cr atoms exhibit a bonding preference for each other and are surrounded by Zn atoms. Smaller Cr 2 Zn x ( x ≤ 5) clusters predominantly adopt bipyramidal geometries, while larger clusters ( x = 8–11 and x = 13–18) are based on the tri‐capped trigonal prism and hexagonal antiprismatic structures, respectively. ICSS analysis confirms the aromatic character of the Cr 2 Zn 9 cluster, while AdNDP analysis further reveals its dual (σ and π) aromaticity. All Cr 2 Zn x ( x = 3–18) clusters are antiferromagnetic, except for the non‐magnetic Cr 2 Zn 12 and ferrimagnetic Cr 2 Zn x ( x = 15, 17, 18) clusters with a total magnetic moment of 2 μ B .