Structural transformations in boron clusters induced by metal doping

Abstract

Would it be possible to eventually derive a simple methodology to predict the structure adopted by boron clusters based on its structural transformation induced by the doping with one or two metal atoms?

From a Möbius-aromatic interlocked Mn2B10H10 wheel to the metal-doped boranaphthalenes M2@B10H8 and M2B5 2D-sheets (M = Mn and Fe): a molecules to materials continuum using DFT studies

“…[2][3][4][23][24][25][26] A parallel development in the gas phase involved the generation of sizeselected boron clusters (B n ) and metal-boron clusters (M x B n ) with different types of multicentered bonding (e.g., V-VIII). [5][6][7][27][28][29][30][31][32] Although the absence of ligands in VI distinguishes its chemical bonding from IV, the unique p-bonding is important in both. 33,34 The structural variations of B n and M x B n clusters largely depend on the size of the atoms.…”

“…, V–VIII). 5–7,27–32 Although the absence of ligands in VI distinguishes its chemical bonding from IV, the unique π-bonding is important in both. 33,34 The structural variations of B n and M x B n clusters largely depend on the size of the atoms.…”

Be4B12+: A Covalently Bonded Archimedean Beryllo‐Borospherene

“…Lanthanides or transition metals have filled f and/ or d electrons to be donated to the vacant p orbitals of boron to form strong interactions, and therefore, such interactions cause to reshape the boron moiety, facilitating the orbital overlap with the dopants. [24][25][26] Now, the question is whether the main-group elements can also induce such a drastic structural alteration in boron clusters since the experimental use of lanthanides or transition metals is very expensive. From previous experience in Li n B 12 (n = 1-3) clusters, [27] we know that the electron transfer from electropositive elements can cause a structural transition from one shape to another.…”

Bowl‐shaped Cluster CuB12−: A Viable Global Minimum with Twofold Aromaticity

“…The energy decomposition analysis suggests that the energetic cost of distorting the B 12 quasi‐planar fragment is overcompensated by an enhanced electrostatic interaction between the Li cations and the tubular or cage‐like B 12 fragments main reason for such drastic structural changes. A recently published review summarizes the findings on the effects on boron clusters when doped with different metals [44] …”

“…A recently published review summarizes the findings on the effects on boron clusters when doped with different metals. [44] The question we want to address here is, what about transition metals that can transfer one electron to the B 12 backbone? The obvious candidates are the group 11 elements (Cu, Ag, Au), which form compounds with oxidation states of + 1.…”