High-Pressure Synthesis of Cyclic Phosphazenes by Near-UV Photoinduced Reactivity of NH3 and Elemental Phosphorus,The Journal of Physical Chemistry C

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High-Pressure Synthesis of Cyclic Phosphazenes by Near-UV Photoinduced Reactivity of NH3 and Elemental Phosphorus
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2020-01-23 , DOI: 10.1021/acs.jpcc.9b11462
Demetrio Scelta _{1,

2} , Adhara Baldassarre _{1,

3} , Manuel Serrano-Ruiz ₂ , Alexey Marchuk ₄ , Sebastian Vogel ₄ , Wolfgang Schnick ₄ , Maurizio Peruzzini ₂ , Roberto Bini _{1,

2,

3} , Matteo Ceppatelli _{1,

2}

Affiliation

A comparison between the high-pressure (0.8 GPa) photoinduced reactivity of black and red phosphorus at ambient temperature in the presence of ammonia has been conducted in diamond anvil cells (DACs), using spectroscopy (IR and Raman) and X-ray diffraction (XRD). Reactivity has been triggered exploiting the two-photon absorption of near-UV radiation by ammonia. The infrared characterization showed a very complex reactivity in the case of red phosphorus, proceeding to a much higher extent with respect to the black allotrope. Furthermore, Raman spectra showed the formation of molecular hydrogen and phosphine besides three different solid products. Whereas one of them is air sensitive, the other two are recoverable at ambient conditions. IR, Raman, and XRD data for the obtained products have been compared to those acquired on known H_xP_yN_z compounds: for one of the two stable products, a fair matching was found with the XRD pattern and the IR spectrum of P₃N₃(NH₂)₆·(NH₃)_0.5, whereas for the other one only the functional groups actually involved in the structure could be evinced from accurate Raman mapping of the sample, with no further information about composition or stoichiometry. High density conditions in combination with near-UV laser irradiation were thus proved to be effective in the formation of two stable reaction products featuring new P–N functionalities, both recoverable at ambient pressure. For the first time, a cyclic triphosphazene has been synthesized through the reaction of red phosphorus and ammonia triggered by UV light under moderate high-pressure conditions, possibly opening new perspectives about this topic.

中文翻译：

近紫外光诱导的NH ₃和元素磷的反应性高压合成环磷酸酯

使用光谱仪（IR和Raman）和X射线衍射仪（DAC）在金刚石砧室（DAC）中进行了在环境温度下氨存在下高压（0.8 GPa）的黑磷和红磷在室温下光诱导的反应性的比较（ XRD）。利用氨对近紫外辐射的双光子吸收已经触发了反应性。在红磷的情况下，红外表征显示出非常复杂的反应性，相对于黑色同素异形体而言，进行的程度更高。此外，拉曼光谱显示除了三种不同的固体产物外还形成了分子氢和膦。其中一个对空气敏感，而另两个在环境条件下可恢复。将获得的产品的IR，拉曼和XRD数据与在已知H上获得的数据进行比较_x P_y N_z化合物：对于两种稳定产物之一，发现X射线衍射图和P₃ N₃（NH₂）₆ ·（NH₃）_0.5的红外光谱具有合理的匹配性，而对于另一种，只有样品的准确拉曼作图可以证明结构中实际涉及的官能团，而没有关于组成或化学计量的进一步信息。因此，高密度条件与近紫外激光辐照相结合，可有效地形成两种具有新的PN功能的稳定反应产物，两者均可在环境压力下回收。第一次，环状三磷腈通过在中等高压条件下由紫外光触发的红磷和氨的反应合成，可能为该主题开辟新的前景。

更新日期：2020-01-24

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