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Abstract

Density-functional theory based global geometry optimization is used to scrutinize the possibility of using endohedrally doped hydrogenated Si clusters as building blocks for constructing highly magnetic materials. In contrast to the known clathrate-type facet-sharing, the clusters exhibit a predisposition to aggregation through double Si–Si bridge bonds. For the prototypical CrSi₂₀H₂₀ cluster we show that reducing the degree of hydrogenation may be used to control the number of reactive sites to which other cages can be attached, while still preserving the structural integrity of the building block itself. This leads to a toolbox of CrSi₂₀H_20–2n monomers with different number of double “docking sites”, that allows building network architectures of any morphology. For (CrSi₂₀H₁₈)₂ dimer and [CrSi₂₀H₁₆](CrSi₂₀H₁₈)₂ trimer structures we illustrate that such aggregates conserve the high spin moments of the dopant atoms and are therefore most attractive candidates for cluster-assembled materials with unique magnetic properties. The study suggests that the structural completion of the individual endohedral cages within the doubly bridge bonded structures and the high thermodynamic stability of the obtained aggregates are crucial for potential synthetic polimerization routes via controlled dehydrogenation.