Monitoring photo-induced population dynamics in metastable linkage isomer crystals: a crystallographic kinetic study of [Pd(Bu4dien)NO2]BPh4

• Published in: Physical chemistry chemical physics : PCCP Vol. 20; no. 8; pp. 5874 - 5886
• Main Authors: Hatcher, Lauren E, Skelton, Jonathan M, Warren, Mark R, Stubbs, Clare, Lora da Silva, E, Raithby, Paul R
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 2018
• Subjects: Computer simulation; Crystallography; Kinetics; Nitrogen dioxide; Single crystals; Temperature dependence; X-ray diffraction
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/c7cp05422j

We present a detailed kinetic study of photo-induced solid state linkage isomerism in the compound [Pd(Bu4dien)NO2]BPh4 (Bu4dien = 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.