Spin accommodation and reactivity of nickel clusters with oxygen:Aromatic and magnetic metalloxocube Ni13O8±

作者:

L GengB YinH ZhangZD SunZ Luo

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摘要:

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 Ni_(13)O_(8)±that dominate the mass distributions.By quantum chemistry calculations,we find that both Ni_(13)O_(8)and Ni_(13)O_(8)+clusters bear a regular cubic structure with 8 oxygen anchoring the eight angles,however,they have rather different spin accommodations.The Ni_(13)O_(8)clusters have 15 unpaired spin-up electrons exhibiting cubic aromaticity and decent ferromagnetism,while the Ni_(13)O_(8)+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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年份:

2021

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