Hatcher Lauren E, Skelton Jonathan M, Warren Mark R, Stubbs Clare, da Silva E Lora, Raithby Paul R
Department of Chemistry, University of Bath, Bath, BA2 7AY, UK.
Phys Chem Chem Phys. 2018 Feb 21;20(8):5874-5886. doi: 10.1039/c7cp05422j.
We present a detailed kinetic study of photo-induced solid state linkage isomerism in the compound [Pd(Budien)NO]BPh (Budien = N,N,N',N'-tetrabutyldiethylenetriamine) using in situ photocrystallographic techniques. We explore the key variables that influence the photoconversion and develop a detailed kinetic model for the excitation and decay processes and the temperature dependence of the conversion rates. We show that by varying the temperature the lifetime of the excited state can be varied over orders of magnitude, making these systems ideal test cases for the development of new time-resolved X-ray diffraction methods. The kinetic model is used to build a numerical-simulation tool, which we use to explore the practicalities of pump-probe single-crystal diffraction experiments with minute and second time-resolution.
我们使用原位光晶体学技术，对化合物[Pd(Budien)NO]BPh（Budien = N,N,N',N'-四丁基二亚乙基三胺）中的光诱导固态键合异构现象进行了详细的动力学研究。我们探究了影响光转化的关键变量，并针对激发和衰减过程以及转化率的温度依赖性建立了详细的动力学模型。我们表明，通过改变温度，激发态的寿命可以在几个数量级范围内变化，这使得这些系统成为开发新的时间分辨X射线衍射方法的理想测试案例。动力学模型被用于构建一个数值模拟工具，我们用它来探索具有微秒和秒级时间分辨率的泵浦-探测单晶衍射实验的实用性。
