Time-resolved single-crystal X-ray crystallography

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 single-crystalline nature of the solid may be preserved. Because of this photoactivation, time-resolved crystallography is often described as “photocrystallography”. The initial photocrystallographic studies were carried out on molecular complexes that either underwent irreversible photoactivated processes where the conversion took hours or days. Structural snapshots were taken during the process. Materials that achieved a metastable state under photoactivation and the excited (metastable) state had a long enough lifetime for the data from the crystal to be collected and the structure solved. For systems with shorter lifetimes, the first time-resolved results were obtained for macromolecular structures, where pulsed lasers were used to pump up the short lifetime excited state species and their structures were probed by using synchronised X-ray pulses from a high-intensity source. Developments in molecular crystallography soon followed, initially with monochromatic X-ray radiation, and pump-probe techniques were used to establish the structures of photoactivated molecules with lifetimes in the micro- to millisecond range. For molecules with even shorter lifetimes in the sub-microsecond range, Laue diffraction methods (rather than using monochromatic radiation) were employed to speed up the data collections and reduce crystal damage. Future developments in time-resolved crystallography are likely to involve the use of XFELs to complete “single-shot” time-resolved diffraction studies that are already proving successful in the macromolecular crystallographic field.</p

Dynamic and static muon-spin relaxation observed above and below the spin-crossover in Fe(II) complexes

The spin-crossover phenomenon is a cooperative low-spin (LS) to high-spin (HS) transition which can be initiated using temperature or light irradiation. We have used muon-spin relaxation (muSR) to study this transition in two salts which show this effect. muSR provides local magnetic information and hence a means of examining this transition from a local perspective. For both salts, the LS phase gives rise to root-exponential relaxation which we associate with a dilute distribution of fluctuating moments resulting from incomplete spin crossover. The low temperature HS fraction which remains is small but can be altered by rapid cooling. We relate the observed muon relaxation to the underlying fluctuating moment distribution and compare our results to Monte-Carlo simulations of these distributions

Characterization of a boro-silicon oxynitride prepared by thermal nitridation of a polyborosiloxane

Fine physicochemical characterization has allowed proposing of a mechanism for the nitridation pathway of a polyborosiloxane polymer into a new ceramic material in the SiBON system. A polyborosiloxane, a polymer consisting of Si-O-B linkages, was synthesized by the condensation reaction between tetrachlorosilane SiCl4 and boric acid B(OH)(3). The polymer was then thermally nitridated under flowing ammonia into an oxynitride of boron and silicon. This conversion was observed using various structural techniques: chemical analysis, X-ray diffraction, infrared spectroscopy and X-ray photoelectron spectroscopy. The nitridation process can be divided in two main stages: (i) between 400 and 800 degrees C, B-N bonds are formed by B-O bond cleavage; (ii) above 1000 degrees C, Si-N bonds are formed by Si-O bond cleavage, The oxynitride remains amorphous even at 1300 degrees C. Pyrolysis up to 1700 degrees C led to a partial crystallization of hexagonal boron nitride