The advance of electron crystallographic techniques during the last decade has had a significant impact on the structural analysis of micro- and nanocrystalline materials. 3D electron diffraction and atomic-resolution imaging are cornerstones of electron crystallography. In the chapter “Structural studies of inorganic materials by electron crystallography” we cover a broad range of topics, from the principles of image and diffraction pattern formation inside a transmission electron microscope, to recent advances in data collection and processing, making possible ab-initio crystal structure solution as well as in-depth microstructural investigations from μm- and nm-size regions of inorganic materials. We focus on obtaining detailed structural information at atomic resolution, which is essential for developing new materials, optimizing their properties and utilizing their full functionality.

The structure of zeolite SSZ-43 was determined by 3D electron diffraction, synchrotron X-ray powder diffraction, and high-resolution transmission electron microscopy. The SSZ-43 framework forms one-dimensional, sinusoidal 12-ring channels from 5461 butterfly units commonly found in other zeolites, but with unique 6.5×6.5 Å apertures and 12-ring 6.5×8.9 Å windows perpendicular to the channels. SSZ-43 crystals are intergrowths of two polytypes: ≈90 % orthorhombic polytype A with ABAB stacking of the 12-rings, and ≈10 % monoclinic polytype B with ABCABC stacking. Molecular modeling performed on the idealized Si-SSZ-43 structure along with empirical relationships for zeolite selectivity in boron- and aluminum-containing synthesis gels were used in a combined approach to design new di-quaternary ammonium organic structure-directing agents (OSDAs). Experimental trials demonstrated that the new OSDAs produced SSZ-43 over a broader range of compositions than previous mono-quaternary OSDAs.

DUT-8(Ni) metal–organic framework (MOF) belongs to the family of flexible pillared layer materials. The desolvated framework can be obtained in the open pore form (op) or in the closed pore form (cp), depending on the crystal size regime. In the present work, we report on the behaviour of desolvated DUT-8(Ni) at elevated temperatures. For both, op and cp variants, heating causes a structural transition, leading to a new, crystalline compound, containing two interpenetrated networks. The state of the framework before transition (op vs. cp) influences the transition temperature: the small particles of the op phase transform at significantly lower temperature in comparison to the macroparticles of the cp phase, transforming close to the decomposition temperature. The new compound, confined closed pore phase (ccp), was characterized by powder X-ray diffraction and spectroscopic techniques, such as IR, EXAFS, and positron annihilation lifetime spectroscopy (PALS). Thermal effects of structural transitions were studied using differential scanning calorimetry (DSC), showing an overall exothermic effect of the process, involving bond breaking and reformation. Theoretical calculations reveal the energetics, driving the observed temperature induced phase transition. 

Transition metal trichlorides show peculiar and versatile magnetic properties. Whereas CrCl3 is a layered antiferromagnet with potential applications as an ultrathin two-dimensional magnet, α−RuCl3 may host a spin-liquid state driven by Kitaev interactions. The interest to control their material properties by chemical modifications is immense, both from an application related and from a fundamental point of view. Here, by studying CrCl3, Cr0.5Ru0.5Cl3, and α−RuCl3 by photoemission and electron energy-loss spectroscopy, we find that transition metal substitution changes the optical properties of the host without compromising its underlying electronic structure. It does so by a Cr–Ru related charge transfer process across the Mott gap effectively opening up a new absorption channel below the principal gap edge of CrCl3. The Cr and Ru valencies as well as the respective valence band density of states remain stable for the mixed Cr0.5Ru0.5Cl3 compound. Our study underlines the potential of transition metal substitution as a means of material engineering of trichlorides.

We report a comprehensive high-field/high-frequency electron spin resonance (ESR) study on single crystals of the van der Waals magnet CrCl3. This material, although being known for quite a while, has received recent significant attention in a context of the use of van der Waals magnets in novel spintronic devices. Temperature-dependent measurements of the resonance fields were performed between 4 and 175 K and with the external magnetic field applied parallel and perpendicular to the honeycomb planes of the crystal structure. These investigations reveal that the resonance line shifts from the paramagnetic resonance position already at temperatures well above the transition into a magnetically ordered state. Thereby the existence of ferromagnetic short-range correlations above the transition is established and the intrinsically two-dimensional nature of the magnetism in the title compound is proven. To study details of the magnetic anisotropies in the field-induced effectively ferromagnetic state at low temperatures, frequency-dependent ferromagnetic resonance (FMR) measurements were conducted at 4 K. The observed anisotropy between the two magnetic-field orientations is analyzed by means of numerical simulations based on a phenomenological theory of FMR. These simulations are in excellent agreement with measured data if the shape anisotropy of the studied crystal is taken into account, while the magnetocrystalline anisotropy is found to be negligible in CrCl3. The absence of a significant intrinsic anisotropy thus renders this material as a practically ideal isotropic Heisenberg magnet.

A DigitalMicrograph script, InsteaDMatic, has been developed to facilitate rapid automated 3D electron diffraction/microcrystal electron diffraction data acquisition by continuous rotation of a crystal with a constant speed, denoted as continuous rotation electron diffraction. The script coordinates microscope functions, such as stage rotation, and camera functions relevant for data collection, and stores the experiment metadata. The script is compatible with any microscope that can be controlled by DigitalMicrograph and has been tested on both JEOL and Thermo Fisher Scientific microscopes. A proof of concept has been performed through employing InsteaDMatic for data collection and structure determination of a ZSM-5 zeolite. The influence of illumination settings and electron dose rate on the quality of diffraction data, unit-cell determination and structure solution has been investigated in order to optimize the data acquisition procedure.

Endohedral cluster compounds are a rich source of new superconductors, where nontrivial properties are expected, including strong coupling regime and multigap superconductivity. Here, we report on the synthesis, crystal and electronic structure, and physical properties of the Mo6Ga31 endohedral cluster superconductor. The compound has two crystallographic modifications, monoclinic and triclinic, which are built by the Mo@Ga-10 endohedral clusters. Both structures possess qualitatively the same electronic density of states showing a high peak at the Fermi level. Due to the proximity effect of the triclinic and monoclinic domains, which are in the strong contact with each other, bulk Mo6Ga31 exhibits single superconducting transition at the critical temperature of 8.2 K in zero magnetic field. The upper critical field, which is 7.8 T at zero temperature, shows clear enhancement with respect to the WerthamerHelfand-Honenberg prediction. Accordingly, heat capacity measurements indicate strong electron-phonon coupling in the superconducting state with the large ratio of 2 Delta(0)/(k(B)T(c)) = 4.5, where 2 Delta(0) = 3.2 meV is the full superconducting gap at zero temperature.

Encapsulation and confinement of fullerene guests in metal-organic frameworks (MOFs) lead to a novel class of crystalline fulleretic materials with unique physicochemical properties and a broad field of potential applications. The control over the amount of target guests confined in the MOF structure remains a significant challenge, which is particularly pronounced in the confinement of hardly accessible fullerene derivatives. The main strategies used in constructing fulleretic composites are limited by the solubility of components used and solvent versus guest competition for inhabitation of the framework voids. As mechanochemical procedures often overcome these issues, we developed here solvent-free processing by ball milling to gain control over the encapsulation of bulky and rigid C-60-fullerene into a sodalite MOF with large cages and narrow cage-apertures. A rapid, green, efficient, and stoichiometry-controlled mechanochemical processing afforded four model C-60@zeolitic-imidazolate framework 8 (ZIF-8) crystalline materials containing target 15, 30, 60, and 100 mol % of fullerene entrapped in the accessible cages of the model sodalite zeolitic-imidazolate framework 8 (ZIF-8), in stark contrast to the solution-based strategies that resulted in almost no loading. Varying the fullerene content affects the framework's vibrational properties, color and luminescence of the composites, and the electron-dose radiation stability. The computational and spectroscopic studies show that the fullerene is accommodated in the cage's center and that the cage-to-cage transport is a hardly feasible and energetically unfavored process. However, the fast release of C-60 molecules from ZIF-8 can be effectively controlled by the pH. The entrapment of fullerene molecules in ZIF-8 resulted in their effective isolation even in higher loadings, paving the way to other tunable porous fulleretics containing single-molecule magnets or nanoprobes available on low scales.

Magnetic properties of the substitution series Ru1-xCrxCl3 were investigated to determine the evolution from the anisotropic Kitaev magnet alpha-RuCl3 with J(eff) = 1/2 magnetic Ru(3+ )ions to the isotropic Heisenberg magnet CrCl3 with S = 3/2 magnetic Cr3+ ions. Magnetization measurements on single crystals revealed a reversal of the magnetic anisotropy under doping, which we argue to arise from the competition between anisotropic Kitaev and off-diagonal interactions on the Ru-Ru links and approximately isotropic Cr-Ru and isotropic Cr-Cr interactions. In addition, combined magnetization, ac susceptibility, and specific-heat measurements clearly show the destabilization of the long-range magnetic order of alpha-RuCl3 in favor of a spin-glass state of Ru1-xCrxCl3 for a low doping of x similar or equal to 0.1. The corresponding freezing temperature as a function of Cr content shows a broad maximum around x similar or equal to 0.45.