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Metal-encapsulated silicon cage clusters are a new class of clusters and are opening up new avenues for silicon-based nanoscale materials. We present experimental evidence for a highly stable cluster corresponding to M@Si16 (M = Sc, Ti, and V). Mass spectrometry and anion photoelectron spectroscopy show that the cluster features an electronically closed TiSi16 neutral core which undergoes a change in the number of valence electrons involving (i) substitution of neighboring metals with Sc and V, or (ii) addition of a halogen atom to the TiSi16 anion, and that VSi16F is predicted to form an ionically bound superatom complex.
Koyasu et al. (Fri,) studied this question.