Struct Bond (2020) 185: 239–272
https://doi.org/10.1007/430_2020_74
# Springer Nature Switzerland AG 2020
Published online: 4 October 2020
Time-Resolved Single-Crystal X-Ray
Crystallography
Paul R. Raithby
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
2 Photocrystallographic Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
2.1 Steady-State and Pseudo-Steady-State Methodologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
2.2 Stroboscopic or Pump-Probe Methodologies . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . .. . . . . . . . 245
2.3 Laue Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
2.4 Sub-picosecond and XFEL Methodologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
3 The Beginnings of Time-Resolved Crystallography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
3.1 Macromolecular Photocrystallography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
3.2 Molecular Photocrystallography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
3.3 Time-Resolved Molecular Photocrystallographic Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
Abstract In this chapter the development of time-resolved crystallography is traced
from its beginnings more than 30 years ago. The importance of being able to “watch”
chemical processes as they occur rather than just being limited to three-dimensional
pictures of the reactant and final product is emphasised, and time-resolved crystallography provides the opportunity to bring the dimension of time into the crystallographic experiment. The technique has evolved in time with developments in
technology: synchrotron radiation, cryoscopic techniques, tuneable lasers, increased
computing power and vastly improved X-ray detectors. The shorter the lifetime of
the species being studied, the more complex is the experiment. The chapter focusses
on the results of solid-state reactions that are activated by light, since this process
does not require the addition of a reagent to the crystalline material and the singlecrystalline nature of the solid may be preserved. Because of this photoactivation,
time-resolved crystallography is often described as “photocrystallography”.
P. R. Raithby (*)
Department of Chemistry, University of Bath, Bath, UK
e-mail: p.r.raithby@bath.ac.uk
https://doi.org/10.1007/430_2020_74
# Springer Nature Switzerland AG 2020
Published online: 4 October 2020
Time-Resolved Single-Crystal X-Ray
Crystallography
Paul R. Raithby
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
2 Photocrystallographic Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
2.1 Steady-State and Pseudo-Steady-State Methodologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
2.2 Stroboscopic or Pump-Probe Methodologies . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . .. . . . . . . . 245
2.3 Laue Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
2.4 Sub-picosecond and XFEL Methodologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
3 The Beginnings of Time-Resolved Crystallography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
3.1 Macromolecular Photocrystallography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
3.2 Molecular Photocrystallography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
3.3 Time-Resolved Molecular Photocrystallographic Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
Abstract In this chapter the development of time-resolved crystallography is traced
from its beginnings more than 30 years ago. The importance of being able to “watch”
chemical processes as they occur rather than just being limited to three-dimensional
pictures of the reactant and final product is emphasised, and time-resolved crystallography provides the opportunity to bring the dimension of time into the crystallographic experiment. The technique has evolved in time with developments in
technology: synchrotron radiation, cryoscopic techniques, tuneable lasers, increased
computing power and vastly improved X-ray detectors. The shorter the lifetime of
the species being studied, the more complex is the experiment. The chapter focusses
on the results of solid-state reactions that are activated by light, since this process
does not require the addition of a reagent to the crystalline material and the singlecrystalline nature of the solid may be preserved. Because of this photoactivation,
time-resolved crystallography is often described as “photocrystallography”.
P. R. Raithby (*)
Department of Chemistry, University of Bath, Bath, UK
e-mail: p.r.raithby@bath.ac.uk