Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 137, Issue 12, Pages 4207-4214Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b00998
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Funding
- National Science Foundation
- Ohio Supercomputer Center
- Ministry of Education, Culture, Sports, Science and Technology, Japan [24109008]
- Grants-in-Aid for Scientific Research [24109008] Funding Source: KAKEN
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1057481] Funding Source: National Science Foundation
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The photolysis of 2-azido-1,4-naphthoquinone (1) in argon matrices at 8 K results in the corresponding triplet vinylnitrene (3)2, which was detected directly by IR spectroscopy. Vinylnitrene (3)2 is stable in argon matrices but forms 2-cyanoindane-1,3-dione (3) upon further irradiation. Similarly, the irradiation of azide 1 in 2-methyltetrahydrofuran (MTHF) matrices at 5 K resulted in the ESR spectrum of vinylnitrene (3)2, which is stable up to at least 100 K. The zero-field splitting parameters for nitrene (3)2, D/hc = 0.7292 cm(-1) and E/hc = 0.0048 cm(-1), verify that it has significant 1,3-biradical character. Vinylnitrene (3)2 (lambda(max) similar to 460 nm, tau = 22 mu s) is also observed directly in solution at ambient temperature with laser flash photolysis of 1. Density functional theory (DFT) calculations support the characterization of vinylnitrene (3)2 and the proposed mechanism for its formation. Because vinylnitrene (3)2 is relatively stable, it has potential use as a building-block for high-spin assemblies.
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