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Unlocking a diazirine long-lived nuclear singlet state via photochemistry: NMR detection and lifetime of an unstabilized diazo-compound

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JournalJournal of the American Chemical Society
DateAccepted/In press - 8 Nov 2018
DateE-pub ahead of print - 8 Nov 2018
DatePublished (current) - 5 Dec 2018
Issue number48
Number of pages10
Pages (from-to)16855-16864
Early online date8/11/18
Original languageEnglish


Diazirines are important for photoaffinity labelling and their photoisomerization is relatively well known. This work shows how hyperpolarized NMR spectroscopy can be used to characterise an unstable diazo-compound formed via photoisomerization of a 15N2-labelled silyl-ether substituted diazirine. This diazirine is prepared in a nuclear spin singlet state via catalytic transfer of spin order from para-hydrogen. The active hyperpolarization catalyst is characterised to provide insight into the mechanism. The photochemical isomerisation of the diazirine into the diazo-analogue allows the NMR invisible nuclear singlet state of the parent compound to be probed. The identity of the diazo-species is confirmed by trapping with N-phenyl maleimide via a cycloaddition reaction to afford bicyclic pyrazolines that also show singlet state character. The presence of singlet states in the diazirine and the diazo-compound are validated by comparison of experimental nutation behaviour with theoretical simulation. The magnetic state lifetime of the diazo-compound is determined as 12 ± 1 s in CD3OD solution at room temperature whereas its chemical lifetime is measured as 100 ± 5 s by related hyperpolarized NMR studies. Indirect evidence for the
generation of the photoproduct para-N2 is presented.

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© 2018 American Chemical Society

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