A systematic structure and property investigation of MnGen− (n = 3–14) was conducted by means of density functional theory coupled with mass-selected anion photoelectron spectroscopy. This combined theoretical and experimental study allows global minimum and coexistence structures to be identified. It is found that the pentagonal bipyramid shape is the basic framework for the nascent growth process of MnGen− (n = 3–10), and from n = 10, the endohedral structures can be found. For n = 12, the anion MnGe12− cluster probably includes two isomers: a major isomer with a puckered hexagonal prism geometry and a minor isomer with a distorted icosahedron geometry. Specifically, the puckered hexagonal prism isomer follows the Wade–Mingos rules and can be suggested as a new kind of superatom with the magnetic property. Furthermore, the results of adaptive natural density partitioning and deformation density analyses suggest a polar covalent interaction between Ge and Mn for endohedral clusters of MnGe12−. The spin density and natural population analysis indicate that MnGen− clusters have high magnetic moments localized on Mn. The density of states diagram visually shows the significant spin polarization for endohedral structures and reveals the weak interaction between the Ge 4p orbital and the 4s, 3d orbitals of Mn.

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Lanthanide doped silicon clusters have been extensively studied in the fields of optoelectronics, magnetism and nanomaterials during last decade. Herein, the systematic structure searches for typical neutral clusters of lanthanide...

One-dimensional (1D) atomic chains that exhibit large magnetic anisotropy are highly relevant to spintronic applications. Such 1D magnetic systems have usually been produced by atom/molecular assembling on solid surfaces or by coordination polymers. Here, we demonstrate an alternative approach for the formation of a confined ferromagnetic holmium (Ho) atom chain, which is composed of repeating units of the tubular Ho doped boron (B) cluster HoB20. The tubular HoB20 is discovered by the global structural search of a series of small-sized boron clusters doped by a single Ho atom (HoB n , n = 12, 14, 16, 18, 20) using ab initio calculations. Electronic analysis reveals that the individual HoB20 cluster is stabilized by the double σ + π aromaticity. Extending the tubular structure results in a single Ho atom chain being confined inside a boron nanotube, which shows ferromagnetic behaviors and a large magnetic anisotropy of more than 40 meV/atom. Our findings indicate that the magnetic lanthanide chain is a promising candidate for high-density magnetic information storage.