期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 135, 期 39, 页码 14670-14678出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja405284t
关键词
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资金
- National Science Foundation American Competitiveness in Chemistry Fellowship [CHE-1137284]
- University of Ottawa
- CCRI
- NSERC
- Early Researcher Award
- CFI
- ORF
- FFCR
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1137284] Funding Source: National Science Foundation
One-electron oxidation or reduction of the paramagnetic dinuclear Co(II) complex dmp(2)Nin{Co[N(SiMe3)(2)]}(2) (1; dmp(2)Nin(2-) = bis(2,6-dimethylphenyl)nindigo), by fully reversible chemical or electrochemical methods, generates the radical salts [1(OEt2)](+) and [1](-), respectively. Full structural and magnetic analyses reveal the locus of the redox changes to be nindigo-based, thus giving rise to ligand-centered radicals sandwiched between two paramagnetic and low coordinate Co(II) centers. The presence of these sandwiched radicals mediates magnetic coupling between the high-spin (S = 3/2) cobalt ions, which gives rise to single-molecule magnet (SMM) activity in both the oxidized ([1(OEt2)](+)) and reduced ([1](-)) states. This feature represents the first example of a SMM exhibiting fully reversible, dual ON/OFF switchability in both the cathodic and anodic states.
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