Small-rotative fixed-target serial synchrotron crystallography (SR-FT-SSX) for molecular crystals.

The increasing availability of ultrabright Light Sources is facilitating the study of smaller crystals at faster timescales but with an increased risk of severe X-ray damage, leading to developments in multi-crystal methods such as serial crystallography (SX). SX studies on crystals with small unit cells are challenging as very few reflections are recorded in a single data image, making it difficult to determine the orientation matrix for each crystal and thus preventing the combination of the data from all crystals for structure solution. We herein present a Small-Rotative Fixed-Target Serial Synchrotron Crystallography (SR-FT-SSX) methodology, in which rotation of the serial target through a small diffraction angle at each crystal delivers high-quality data, facilitating ab initio unit cell determination and atomic-scale structure solution.

Exploring Pyroelectricity, Thermal and Photochemical Switching in a Hybrid Organic-Inorganic Crystal by In Situ X-Ray Diffraction.

The switching behavior of the novel hybrid material (FA)Na[Fe(CN)(NO)].HO (1) in response to temperature (T), light irradiation and electric field (E) is studied using in situ X-ray diffraction (XRD). Crystals of 1 display piezoelectricity, pyroelectricity, second and third harmonic generation.

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

We present a charge density study of two linkage isomer photoswitches, [Pd(Budien)(NO)]BPh·THF (1) and [Ni(Etdien)(NO)] (2) using Hirshfeld Atom Refinement (HAR) methods implemented the NoSpherA2 interface in Olex2. HAR is used to explore the electron density distribution in the photoswitchable molecules of 1 and 2, to gain an in-depth understanding of key bonding features and their influence on the single-crystal-to-single-crystal reaction. HAR analysis is also combined with calculations to explore the non-covalent interactions that influence physical properties of the photoswitches, such as the stability of the excited state nitrito-(-ONO) isomer.

Enhancing the repeatability and sensitivity of low-cost PCB, pH-sensitive field-effect transistors.

Discrete, extended gate pH-sensitive field-effect transistors (dEGFETs) fabricated on printed circuit boards (PCBs) are a low-cost, simple to manufacture analytical technology that can be applied to a wide range of applications. Electrodeposited iridium oxide (IrOx) films have emerged as promising pH-sensitive layers owing to their theoretically high pH sensitivity and facile deposition, but typically exhibit low pH sensitivity or lack reproducibility. Moreover, to date, a combined IrOx and dEGFET PCB system has not yet been realised.

LED-pump-X-ray-multiprobe crystallography for sub-second timescales.

The visualization of chemical processes that occur in the solid-state is key to the design of new functional materials. One of the challenges in these studies is to monitor the processes across a range of timescales in real-time. Here, we present a pump-multiprobe single-crystal X-ray diffraction (SCXRD) technique for studying photoexcited solid-state species with millisecond-to-minute lifetimes.

Carbon Nitride as a Ligand: Selective Hydrogenation of Terminal Alkenes Using [(η -C Me )IrCl(g-C N -κ N,N')]Cl.

Anchoring a homogeneous catalyst onto a heterogeneous support facilitates separation of the product from the catalyst, and catalyst-substrate interactions can also modify reactivity. Herein we describe the synthesis of composite materials comprising carbon nitride (g-C N ) as the heterogeneous support and the well-established homogeneous catalyst moiety [Cp*IrCl] (where Cp*=η -C Me ), commonly used for catalytic hydrogenation. Coordination of [Cp*IrCl] to g-C N occurs directly at exposed edge sites with a κ N,N' binding motif, leading to a primary inner coordination sphere analogous to known homogeneous complexes of the general class [Cp*IrCl(NN-κ N,N')] (where N,N'=a bidentate nitrogen ligand).

Carbon nitride as a ligand: edge-site coordination of ReCl(CO)-fragments to g-CN.

IR spectroscopy and model structural studies show binding of ReCl(CO)-fragments to carbon nitride (g-CN) occurs viaκ N,N' bidentate coordination.

Light-Induced Activation of a Molybdenum Oxotransferase Model within a Ru(II)-Mo(VI) Dyad.

Nature uses molybdenum-containing enzymes to catalyze oxygen atom transfer (OAT) from water to organic substrates. In these enzymes, the two electrons that are released during the reaction are rapidly removed, one at a time, by spatially separated electron transfer units. Inspired by this design, a Ru(II)-Mo(VI) dyad was synthesized and characterized, with the aim of accelerating the rate-determining step in the cis-dioxo molybdenum-catalyzed OAT cycle, the transfer of an oxo ligand to triphenyl phosphine, via a photo-oxidation process.