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Issue 8, 2018
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Monitoring photo-induced population dynamics in metastable linkage isomer crystals: a crystallographic kinetic study of [Pd(Bu4dien)NO2]BPh4

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Abstract

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.

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

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Supplementary files

Article information


Submitted
09 Aug 2017
Accepted
29 Jan 2018
First published
31 Jan 2018

This article is Open Access

Phys. Chem. Chem. Phys., 2018,20, 5874-5886
Article type
Paper

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

L. E. Hatcher, J. M. Skelton, M. R. Warren, C. Stubbs, E. L. da Silva and P. R. Raithby, Phys. Chem. Chem. Phys., 2018, 20, 5874
DOI: 10.1039/C7CP05422J

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