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Nuclear Spin Singlet States in Photoactive Molecules: From Fluorescence/NMR Bimodality to a Bimolecular Spin Singlet State Switch
摘要： Nuclear spin singlet states are silent states in nuclear magnetic resonance (NMR). However, they can be probed indirectly and offer great potential for the development of contrast agents for magnetic resonance imaging (MRI). Here, we are introducing two novel concepts: Firstly, we investigate the bimodal NMR/fluorescence properties of 13C2-tetraphenylethylene. It possesses a long-lived singlet state in organic solvents, which shortens upon the addition of water. This simultaneously increases the fluorescence emission in a substantial enhancement of fluorescence. Secondly, we introduce a bimolecular singlet state switch based on 3-2H-coumarin containing an isolated proton. Upon UV-light exposure, a dimer forms leading to a coupling between two previously isolated protons. A nuclear spin singlet state can now be populated. Excitation with a wavelength of 254 nm results in partly cleavage of the molecule back into its monomer.
关键词： Photoswitches,NMR spectroscopy,Aggregation induced emission,Fluorescence,Nuclear spin singlet state
更新于2025-09-23 15:23:52
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Unlocking a diazirine long-lived nuclear singlet state via photochemistry: NMR detection and lifetime of an unstabilized diazo-compound
摘要： 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.
关键词： SABRE-SHEATH,photochemistry,para-hydrogen,diazirine,photoisomerization,nuclear spin singlet state,diazo-compound,hyperpolarized NMR spectroscopy
更新于2025-09-23 15:21:21