Solid-State Photo-NMR Study on Light-Induced Nitrosyl Linkage Isomers Uncovers Their Structural, Electronic, and Diamagnetic Nature.

A light-induced linkage NO isomer (MS1) in trans-[Ru(15NO)(py)419F](ClO4)2 is detected and measured for the first time by solid-state MAS NMR. Chemical shift tensors of 15N and 19F, along with nJ(15N-19F) spin-spin couplings and T1 relaxation times of MS1, are compared with the ground state (GS) at temperatures T < 250 K. Isotropic chemical shifts (15N and 19F) are well resolved for two crystallographically independent cations (A and B) [Ru(15NO)(py)419F]2+, allowing to define separately both populations of MS1 isomers and thermal decay rates for two structural sites. The relaxation times T1 of 19F in the case of GS (30/38.6 s for sites A/B) and MS1 (11.6/11.8 s for sites A/B) indicate that both isomers are diamagnetic, which is the first experimental evidence of diamagnetic properties of MS1 in ruthenium nitrosyl. After light irradiation (λ = 420 nm), the NO ligand rotates by nearly 180° from F-Ru-N-O to F-Ru-O-N, whereby the isotropic chemical shifts of δiso(15N) increase and those of δiso(19F) decrease. The nJ(15N-19F) couplings increase from 2J(15N-Ru-19F)GS = 71 Hz to 3J(15N-O-Ru-19F)MS1 = 105 Hz. These results are interpreted on the basis of DFT-CASTEP calculations including Bader-, Mulliken-, and Hirshfeld-charge density distributions of both states.

In-house time-resolved photocrystallography on the millisecond timescale using a gated X-ray hybrid pixel area detector.

With the remarkable progress of accelerator-based X-ray sources in terms of intensity and brightness, the investigation of structural dynamics from time-resolved X-ray diffraction methods is becoming widespread in chemistry, biochemistry and materials science applications. Diffraction patterns can now be measured down to the femtosecond time-scale using X-ray free electron lasers or table-top laser plasma X-ray sources. On the other hand, the recent developments in photon counting X-ray area detectors offer new opportunities for time-resolved crystallography. Taking advantage of the fast read-out, the internal stacking of recorded images, and the gating possibilities (electronic shutter) of the XPAD hybrid pixel detector, we implemented a laboratory X-ray diffractometer for time-resolved single-crystal X-ray diffraction after pulsed laser excitation, combined with transient optical absorption measurement. The experimental method and instrumental setup are described in detail, and validated using the photoinduced nitrosyl linkage isomerism of sodium nitroprusside, Na2[Fe(CN)5NO]·2H2O, as proof of principle. Light-induced Bragg intensity relative variations ΔI(hkl)/I(hkl) of the order of 1%, due to the photoswitching of the NO ligand, could be detected with a 6 ms acquisition window. The capabilities of such a laboratory time-resolved experiment are critically evaluated.

XPAD X-ray hybrid pixel detector for charge density quality diffracted intensities on laboratory equipment.

The new generation of X-ray detectors, the hybrid pixel area detectors or `pixel detectors', is based on direct detection and single-photon counting processes. A large linearity range, high dynamic and extremely low noise leading to an unprecedented high signal-to-noise ratio, fast readout time (high frame rates) and an electronic shutter are among their intrinsic characteristics which render them very attractive. First used on synchrotron beamlines, these detectors are also promising in the laboratory, in particular for pump-probe or quasi-static experiments and accurate electron density measurements, as explained in this paper. An original laboratory diffractometer made from a Nonius Mach3 goniometer equipped with an Incoatec Mo microsource and an XPAD pixel area detector has been developed at the CRM2 laboratory. Mo Kα accurate charge density quality data up to 1.21 Å(-1) resolution have been collected on a sodium nitroprusside crystal using this home-made diffractometer. Data quality for charge density analysis based on multipolar modelling are discussed in this paper. Deformation electron densities are compared to those already published (based on data collected with CCD APEXII and CAD4 diffractometers).