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Due to challenges in preparing pure metal clusters and in controlling reactions, the oxides produced by metal clusters reacting with oxygen are often different from traditional ion-molecule products in the gas phase and their reactivity pattern is also largely unveiled yet. In this work, utilizing a customized Re-TOFMS having a home-made cluster source and a flow tube reactor, we have observed the gaseous reactions of Nin± clusters with oxygen and found magic clusters of Ni13O8± that dominate the mass distributions. By quantum chemistry calculations, we find that both Ni13O8– and Ni13O8+ clusters bear a regular cubic structure with 8 oxygen anchoring the eight angles, however, they have rather different spin accommodations. The Ni13O8– clusters have 15 unpaired spin-up electrons exhibiting cubic aromaticity and decent ferromagnetism, while the Ni13O8+ clusters take a lower-spin ground state (11 unpaired electrons), with spin-down population on the central Ni atom pertaining to ferrimagnetism. This is a class of metalloxocube clusters that hold properties of aromaticity and ferromagnetism/ferrimagnetism charcterized by a few spin electrons, which embodies the bonding nature of superatomic compounds and enables to develop cluster-genetic materials of multi-functionality.
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