Real‐Time Crystallography of Photoinduced Processes in Supramolecular Framework Solids

Photochemistry and Transmission Pump–Probe Spectroscopy of 2-Azidobiphenyls in Aqueous Nanocrystalline Suspensions: Simplified Kinetics in Crystalline Solids

“…Most mechanistic studies reported to date are based on product analysis combined with single-crystal X-ray diffraction of the reactant, which provide information to correlate the structures of the reactant and the product in order to rationalize the observed reaction trajectory. , A few examples report the use of single-crystal electron paramagnetic resonance − and infrared spectroscopy , to detect the formation and fate of intermediate species. Finally, one of the most elegant but limited strategies involves the use of pulsed laser excitation combined with single-crystal X-ray diffraction to detect reversible reactions occurring upon formation of excited states, reactive intermediates, and photoproducts. − Further progress in the field would benefit strongly from a more general and widely applicable analytical method to study the formation of reactive intermediates and kinetics of reactions in crystals. However, it is known that the spectroscopic analyses of crystals and bulk powders is complicated by their high optical densities, strong light scattering, and the potential interference by the accumulation of photoproducts.…”

Uncovering the role of non-covalent interactions in solid-state photoswitches by non-spherical structure refinements with NoSpherA2

“…the relative kinetic lability of the differing metal centres, and steric inuences from the surrounding crystal lattice. Many of these factors have been discussed by us 5,28,35,36 and others [37][38][39][40][41][42][43] previously, and this conclusion highlights the complexity of rationally-designing solid-state photoswitchable crystals and the importance of considering the many, and oen competing, inuential factors that govern the photoreaction.…”

Stereoelectronic Effects in Cl2 Elimination from Binuclear Pt(III) Complexes

“…The photoinduced structural changes involved in halogen elimination chemistry from Pt 2 [III,III] complex mer- 1 were probed by steady-state photocrystallography experiments. Photocrystallographic analysis is based on generating a photodifference map in which diffraction data collected in the dark is compared with diffraction data collected during steady-state irradiation. − We have previously applied photocrystallography experiments to identify halogen-bridged intermediates in photoelimination from Rh 2 complexes and to elucidate the stereoelectronic effects in M–X bond activation at Ni­(III) trihalide complexes …”