New insights into the sensing mechanism of a phosphonate pyrene chemosensor for TNT†,Physical Chemistry Chemical Physics

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New insights into the sensing mechanism of a phosphonate pyrene chemosensor for TNT†
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2018-06-26 00:00:00 , DOI: 10.1039/c8cp01749b
Meiheng Lu _{1,

2,

3,

4,

5} , Panwang Zhou _{1,

2,

3,

4,

5} , Zhongwei Li _{1,

2,

3,

4,

5} , Jianyong Liu _{1,

2,

3,

4,

5} , Yanqiang Yang _{5,

6,

7,

8,

9} , Keli Han _{1,

2,

3,

4,

5}

Affiliation

As security needs have increased, mechanism investigation has become of high importance in the development of new sensitive and selective chemosensors for chemical explosives. This study details a theoretical investigation of the sensing mechanism of a new phosphonate pyrene chemosensor for trinitrotoluene (TNT), suggesting a different interaction mode between the probe and TNT from the one previously reported. The invalidity of the mechanism of binding TNT through intermolecular hydrogen bonds was proved using the Gibbs free energy profile and ¹H NMR analysis. Frontier molecular orbitals (FMOs) analysis was used to show that photo-induced electron transfer (PET) is the underlying mechanism behind the luminescence quenching of the probe upon exposure to TNT, the rationality of which was further confirmed by the recording of a high charge transfer rate. We also found the existence of an energy level crossing between the local excited (LE) state and charge transfer (CT) state of a complex of the probe and TNT, which was confirmed using energy profile calculations along the linearly interpolated internal coordinate (LIIC) pathway.

中文翻译：

TNT膦pyr化学传感器的传感机制的新见解†

随着安全需求的增加，机制研究在开发用于化学炸药的新型灵敏和选择性化学传感器中变得非常重要。这项研究详细介绍了一种新型膦酸酯pyr化学传感器对三硝基甲苯（TNT）的传感机理的理论研究，表明该探针与TNT之间的相互作用模式与先前报道的不同。通过吉布斯自由能谱和¹证明了通过分子间氢键结合TNT的机理是无效的。1 H NMR分析。前沿分子轨道（FMOs）分析用于显示光致电子转移（PET）是探针在暴露于TNT后发光猝灭的潜在机制，其合理性通过记录高电荷得到了进一步证实传输速率。我们还发现，探针和TNT的复合物在局部激发（LE）状态和电荷转移（CT）状态之间存在能级交叉，这可以通过沿线性内插内坐标（LIIC）进行的能量分布计算来确认途径。

更新日期：2018-06-26

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