Stable Room Temperature Nitrenes Created by Photolysis of Crystalline 4-Azido-2,3,5,6-tetrafluorobenzoic Acid,The Journal of Physical Chemistry C

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Stable Room Temperature Nitrenes Created by Photolysis of Crystalline 4-Azido-2,3,5,6-tetrafluorobenzoic Acid
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2023-02-23 , DOI: 10.1021/acs.jpcc.2c08231
Thomas J. Gately ₁ , Roberto A. Boto ₂ , Michael J. Tauber _{3,

4} , David Casanova _{2,

5} , Christopher J. Bardeen ₁

Affiliation

The structure, spectroscopy, and photochemistry of 4-azidobenzoic acid (4ABC) and its perfluorinated analog 4-azido-2,3,5,6-tetrafluorobenzoic acid (4F4ABC) are characterized in frozen glasses and crystals. Photolysis of the parent azides leads to the production of nitrenes and other spin species that are probed by electron paramagnetic resonance and optical spectroscopy. Shifts in the absorption spectra for both the parent azides and the nitrenes were well reproduced using density functional calculations. Photolysis generates ∼10× higher yield of the triplet nitrene relative to the quintet and radical side-products in 4F4ABC, while the opposite ratio is observed in 4ABC. An annealing step further suppressed the side-products in 4F4ABC, creating a solid where nitrenes were the dominant spin species. The nitrene in the 4F4ABC crystal has a 1/e lifetime of 20 days at room temperature in open air. This stability makes it possible to photopattern nitrene centers into a single crystal and characterize their photoluminescence. Multiple observations suggest that the remarkable stability in the 4F4ABC crystal is a consequence of crystal packing that traps N₂ molecules adjacent to the nitrene. The ability to create stable, solid-state nitrene samples may provide a route to organic high-spin materials with potential applications in spintronics and quantum information science.

中文翻译：

结晶 4-叠氮基-2,3,5,6-四氟苯甲酸光解产生的稳定室温氮烯

4-叠氮基苯甲酸 ( 4ABC ) 及其全氟化类似物 4-叠氮基-2,3,5,6-四氟苯甲酸 ( 4F4ABC ) 的结构、光谱学和光化学在冷冻玻璃和晶体中进行了表征。母体叠氮化物的光解导致氮烯和其他自旋物质的产生，这些物质可通过电子顺磁共振和光谱学进行探测。使用密度泛函计算可以很好地再现母体叠氮化物和氮烯的吸收光谱的变化。相对于4F4ABC中的五重态和自由基副产物，光解产生的三重态氮烯产量高出约 10 倍，而在4ABC中观察到相反的比例。退火步骤进一步抑制了副产物4F4ABC，创建一个固体，其中氮烯是主要的自旋物种。4F4ABC晶体中的氮烯在室温下露天的 1/e 寿命为 20 天。这种稳定性使得将氮烯中心光刻成单晶并表征它们的光致发光成为可能。多项观察表明， 4F4ABC晶体的显着稳定性是晶体堆积的结果，它捕获了与氮烯相邻的N _2分子。创建稳定的固态氮烯样品的能力可能为有机高自旋材料提供一条途径，并在自旋电子学和量子信息科学中具有潜在应用。

更新日期：2023-02-23

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