Chemoselectivity Inversion of Responsive Metal-Organic Frameworks by Particle Size Tuning in the Micrometer Regime.

Gated adsorption is one of the unique physical properties of flexible metal-organic frameworks with high application potential in selective adsorption and sensing of molecules. Despite recent studies that have provided some guidelines in understanding and designing structural flexibility for controlling gate opening by chemical modification of the secondary building units, currently, there is no established strategy to design a flexible MOF showing selective gated adsorption for a specific guest molecule. In a present contribution it is demonstrated for the first time, that the selectivity in the gate opening of a particular compound can be tuned, changed, and even reversed using particle size engineering DUT-8(Zn) ([Zn2 (2,6-ndc)2 (dabco)]n , 2,6-ndc = 2,6-naphthalenedicarboxylate, dabco = 1,4-diazabicyclo-[2.2.2]-octane, DUT = Dresden University of Technology) experiences phase transition from open (op) to closed (cp) pore phase upon removal of solvent from the pores. Microcrystals show selective reopening in the presence of dichloromethane (DCM) over alcohols. Crystal downsizing to micron size unexpectedly reverses the gate opening selectivity, causing DUT-8(Zn) to open its nanosized pores for alcohols but suppressing the responsivity toward DCM.

Molecular replacement for small-molecule crystal structure determination from X-ray and electron diffraction data with reduced resolution.

The resolution of 3D electron diffraction (ED) data of small-molecule crystals is often relatively poor, due to either electron-beam radiation damage during data collection or poor crystallinity of the material. Direct methods, used as standard for crystal structure determination, are not applicable when the data resolution falls below the commonly accepted limit of 1.2 Å. Therefore an evaluation was carried out of the performance of molecular replacement (MR) procedures, regularly used for protein structure determination, for structure analysis of small-molecule crystal structures from 3D ED data. In the course of this study, two crystal structures of Bi-3812, a highly potent inhibitor of the oncogenic transcription factor BCL6, were determined: the structure of α-Bi-3812 was determined from single-crystal X-ray data, the structure of ß-Bi-3812 from 3D ED data, using direct methods in both cases. These data were subsequently used for MR with different data types, varying the data resolution limit (1, 1.5 and 2 Å) and by using search models consisting of connected or disconnected fragments of BI-3812. MR was successful with 3D ED data at 2 Šresolution using a search model that represented 74% of the complete molecule.

Analysis of diffuse scattering in electron diffraction data for the crystal structure determination of Pigment Orange 13, C32H24Cl2N8O2.

The crystallographic study of two polymorphs of the industrial pyrazolone Pigment Orange 13 (P.O.13) is reported. The crystal structure of the ß phase was determined using single-crystal X-ray analysis of a tiny needle. The α phase was investigated using three-dimensional electron diffraction. The electron diffraction data contain sharp Bragg reflections and strong diffuse streaks, associated with severe stacking disorder. The structure was solved by careful analysis of the diffuse scattering, and similarities of the unit-cell parameters with the ß phase. The structure solution is described in detail and this provides a didactic example of solving molecular crystal structures in the presence of diffuse scattering. Several structural models were constructed and optimized by lattice-energy minimization with dispersion-corrected DFT. A four-layer model was found, which matches the electron diffraction data, including the diffuse scattering, and agrees with X-ray powder data. Additionally, five further phases of P.O.13 are described.

Electron-Beam- and Thermal-Annealing-Induced Structural Transformations in Few-Layer MnPS3.

Quasi-two-dimensional (2D) manganese phosphorus trisulfide, MnPS3, which exhibits antiferromagnetic ordering, is a particularly interesting material in the context of magnetism in a system with reduced dimensionality and its potential technological applications. Here, we present an experimental and theoretical study on modifying the properties of freestanding MnPS3 by local structural transformations via electron irradiation in a transmission electron microscope and by thermal annealing under vacuum. In both cases we find that MnS1-xPx phases (0 ≤ x < 1) form in a crystal structure different from that of the host material, namely that of the α- or γ-MnS type. These phase transformations can both be locally controlled by the size of the electron beam as well as by the total applied electron dose and simultaneously imaged at the atomic scale. For the MnS structures generated in this process, our ab initio calculations indicate that their electronic and magnetic properties strongly depend on both in-plane crystallite orientation and thickness. Moreover, the electronic properties of the MnS phases can be further tuned by alloying with phosphorus. Therefore, our results show that electron beam irradiation and thermal annealing can be utilized to grow phases with distinct properties starting from freestanding quasi-2D MnPS3.

Towards a new level of quantitative treatment of 3D electron diffraction data - in-pattern optical distortions.

Electron diffraction patterns unavoidably contain in-plane distortions introduced by electromagnetic lens systems. Geometric correction of different distortion types allows the accuracy of lattice parameter determination to be improved in 3D electron diffraction data.

Evaluation of TEM methods for their signature of the number of layers in mono- and few-layer TMDs as exemplified by MoS2 and MoTe2.

In mono- and few-layer 2D materials, the exact number of layers is a critical parameter, determining the materials' properties and thus their performance in future nano-devices. Here, we evaluate in a systematic manner the signature of exfoliated free-standing mono- and few-layer MoS2 and MoTe2 in TEM experiments such as high-resolution transmission electron microscopy, electron energy-loss spectroscopy, and 3D electron diffraction. A reference for the number of layers has been determined by optical contrast and AFM measurements on a substrate. Comparing the results, we discuss strengths and limitations, benchmarking the three TEM methods with respect to their ability to identify the exact number of layers.

Cooperative Assembly of 2D-MOF Nanoplatelets into Hierarchical Carpets and Tubular Superstructures for Advanced Air Filtration.

Clean air is an indispensable prerequisite for human health. The capture of small toxic molecules requires the development of advanced materials for air filtration. Two-dimensional nanomaterials offer highly accessible surface areas but for real-world applications their assembly into well-defined hierarchical mesostructures is essential. DUT-134(Cu) ([Cu2 (dttc)2 ]n , dttc=dithieno[3,2-b : 2',3'-d]thiophene-2,6-dicarboxylate]) is a metal-organic framework forming platelet-shaped particles, that can be organized into complex structures, such as millimeter large free-standing layers (carpets) and tubes. The structured material demonstrates enhanced accessibility of open metal sites and significantly enhanced H2 S adsorption capacity in gas filtering tests compared with traditional bulk analogues.

Noncovalent Bonding Caught in Action: From Amorphous to Cocrystalline Molecular Thin Films.

We demonstrate the solvent-free amorphous-to-cocrystalline transformations of nanoscale molecular films. Exposing amorphous films to vapors of a haloarene results in the formation of a cocrystalline coating. This transformation proceeds by gradual strengthening of halogen-bonding interactions as a result of the crystallization process. The gas-solid diffusion mechanism involves formation of an amorphous metastable phase prior to crystallization of the films. In situ optical microscopy shows mass transport during this process, which is confirmed by cross-section analysis of the final structures using focused ion beam milling combined with scanning electron microscopy. Nanomechanical measurements show that the rigidity of the amorphous films influences the crystallization process. This surface transformation results in molecular arrangements that are not readily obtained through other means. Cocrystals grown in solution crystallize in a monoclinic centrosymmetric space group, whereas the on-surface halogen-bonded assembly crystallizes into a noncentrosymmetric material with a bulk second-order nonlinear optical response.

Impact of Crystal Size and Morphology on Switchability Characteristics in Pillared-Layer Metal-Organic Framework DUT-8(Ni).

Variation of the crystallite size in flexible porous coordination polymers can significantly influence or even drastically change the flexibility characteristics. The impact of crystal morphology, however, on the dynamic properties of flexible metal-organic frameworks (MOFs) is poorly investigated so far. In the present work, we systematically modulated the particle size of a model gate pressure MOF (DUT-8(Ni), Ni2(2,6-ndc)2(dabco), 2,6-ndc-2,6-naphthalenedicarboxylate, dabco-1,4-diazabicyclo[2.2.2]octane) and investigated the influence of the aspect ratio, length, and width of anisotropically shaped crystals on the gate opening characteristics. DUT-8 is a member of the pillared-layer MOF family, showing reversible structural transition, i.e., upon nitrogen physisorption at 77 K. The framework crystalizes as rod-like shaped crystals in conventional synthesis. To understand which particular crystal surfaces dominate the phenomena observed, crystals similar in size and differing in morphology were involved in a systematic study. The analysis of the data shows that the width of the rods (corresponding to the crystallographic directions along the layer) represents a critical parameter governing the dynamic properties upon adsorption of nitrogen at 77 K. This observation is related to the anisotropy of the channel-like pore system and the nucleation mechanism of the solid-solid phase transition triggered by gas adsorption.

3D electron diffraction of mono- and few-layer MoS2.

Mono- and few-layer MoS2 were studied by three-dimensional electron diffraction (3D ED) showing distinctly different symmetry for crystals consisting of odd and even number of layers. Experimentally obtained intensity distributions along the relrods match qualitatively kinematically simulated data. Our findings allow to differentiate unambiguously between 1-, 2-, 3- 4- and 5-layers MoS2 crystals.

Near-atomic-scale observation of grain boundaries in a layer-stacked two-dimensional polymer.

Two-dimensional (2D) polymers hold great promise in the rational materials design tailored for next-generation applications. However, little is known about the grain boundaries in 2D polymers, not to mention their formation mechanisms and potential influences on the material's functionalities. Using aberration-corrected high-resolution transmission electron microscopy, we present a direct observation of the grain boundaries in a layer-stacked 2D polyimine with a resolution of 2.3 Å, shedding light on their formation mechanisms. We found that the polyimine growth followed a "birth-and-spread" mechanism. Antiphase boundaries implemented a self-correction to the missing-linker and missing-node defects, and tilt boundaries were formed via grain coalescence. Notably, we identified grain boundary reconstructions featuring closed rings at tilt boundaries. Quantum mechanical calculations revealed that boundary reconstruction is energetically allowed and can be generalized into different 2D polymer systems. We envisage that these results may open up the opportunity for future investigations on defect-property correlations in 2D polymers.

Orientational disorder of monomethyl-quinacridone investigated by Rietveld refinement, structure refinement to the pair distribution function and lattice-energy minimizations.

The crystal structure of the organic pigment 2-monomethyl-quinacridone (Pigment Red 192, C21H14N2O2) was solved from X-ray powder diffraction data. The resulting average structure is described in space group P\overline 1, Z = 1 with the molecule on the inversion centre. The molecules are arranged in chains. The molecules, which have no inversion symmetry, show orientational head-to-tail disorder. In the average structure, the methyl group is disordered and found on both ends of the molecule with an occupancy of 0.5 each. The disorder and the local structure were investigated using various ordered structural models. All models were analysed by three approaches: Rietveld refinement, structure refinement to the pair distribution function (PDF) and lattice-energy minimization. All refinements converged well. The Rietveld refinement provided the average structure and gave no indication of a long-range ordering. The refinement to the PDF turned out to be very sensitive to small structural details, giving insight into the local structure. The lattice-energy minimizations revealed a significantly preferred local ordering of neighbouring molecules along the [0\bar 11] direction. In conclusion, all methods indicate a statistical orientational disorder with a preferred parallel orientation of molecules in one direction. Additionally, electron diffraction revealed twinning and faint diffuse scattering.

TEM bright field imaging of thick specimens: nodes in Thon ring patterns.

The thickness of an object will, at some point, exceed the depth of field of a transmission electron microscope; the value at which this occurs, depends on the resolution and the wavelength considered. An image is then no longer a true projection of the 3D structure. This effect will be expressed in the power spectrum. Here, we first demonstrate this phenomenon experimentally, using carbon foils of different thicknesses and working at 40, 60, 80 and 300 kV. Since we determined the thicknesses of the foils by tomography, we are also able to confirm experimentally that in the case of a thick object, the Thon ring pattern can be described as the sum of the power spectra originating from thin, independently scattering slices. Thus, a sinc function envelope is observed that attenuates the Thon rings' amplitudes, yielding "nodes" in the pattern at which the amplitudes are zero. These nodes move to lower spatial frequencies with decreasing acceleration voltages and increasing thicknesses. Conversely, the object thickness can be directly derived from node positions at a particular acceleration voltage. We validate our approach by applying it to frozen-hydrated bacteria with experimentally determined thicknesses. Our model will contribute to more reliably determining the defocus to be used with contrast transfer function correction for thicker objects and at lower acceleration voltages.

3D Electron Diffraction: The Nanocrystallography Revolution.

Crystallography of nanocrystalline materials has witnessed a true revolution in the past 10 years, thanks to the introduction of protocols for 3D acquisition and analysis of electron diffraction data. This method provides single-crystal data of structure solution and refinement quality, allowing the atomic structure determination of those materials that remained hitherto unknown because of their limited crystallinity. Several experimental protocols exist, which share the common idea of sampling a sequence of diffraction patterns while the crystal is tilted around a noncrystallographic axis, namely, the goniometer axis of the transmission electron microscope sample stage. This Outlook reviews most important 3D electron diffraction applications for different kinds of samples and problematics, related with both materials and life sciences. Structure refinement including dynamical scattering is also briefly discussed.

Brodie's or Hummers' Method: Oxidation Conditions Determine the Structure of Graphene Oxide.

Synthesis and studies of graphite oxide started more than 150 years ago and turned into a boom by the measurements of the outstanding physical properties of graphene. A series of preparation protocols emanated trying to optimize the synthesis of graphene oxide in order to obtain a less defective material, as source for graphene. However, over-oxidation of the carbon framework hampered establishing structure-property relationships. Here, the fact that two different synthetic methods for graphene oxide preparation lead to very similar types of graphene oxide with a preserved graphene lattice is demonstrated. Either sodium chlorate in nitric acid (similar to Brodie's method) or potassium permanganate in sulfuric acid (similar to Hummers' method) treatment are possible; however, reaction conditions must be controlled. With a preserved carbon lattice analytical differences between the samples relate to the altered on-plane functionality. Consequently, terming preparation protocols "according to Brodie's/Hummers' method" is not sufficient.

Towards quantitative treatment of electron pair distribution function.

The pair distribution function (PDF) is a versatile tool to describe the structure of disordered and amorphous materials. Electron PDF (ePDF) uses the advantage of strong scattering of electrons, thus allowing small volumes to be probed and providing unique information on structure variations at the nano-scale. The spectrum of ePDF applications is rather broad: from ceramic to metallic glasses and mineralogical to organic samples. The quantitative interpretation of ePDF relies on knowledge of how structural and instrumental effects contribute to the experimental data. Here, a broad overview is given on the development of ePDF as a structure analysis method and its applications to diverse materials. Then the physical meaning of the PDF is explained and its use is demonstrated with several examples. Special features of electron scattering regarding the PDF calculations are discussed. A quantitative approach to ePDF data treatment is demonstrated using different refinement software programs for a nanocrystalline anatase sample. Finally, a list of available software packages for ePDF calculation is provided.

Structure analysis of materials at the order-disorder borderline using three-dimensional electron diffraction.

Diffuse scattering, observed as intensity distribution between the Bragg peaks, is associated with deviations from the average crystal structure, generally referred to as disorder. In many cases crystal defects are seen as unwanted perturbations of the periodic structure and therefore they are often ignored. Yet, when it comes to the structure analysis of nano-volumes, what electron crystallography is designed for, the significance of defects increases. Twinning and polytypic sequences are other perturbations from ideal crystal structure that are also commonly observed in nanocrystals. Here we present an overview of defect types and review some of the most prominent studies published on the analysis of defective nanocrystalline structures by means of three-dimensional electron diffraction.

Crystal structure analysis of a star-shaped triazine compound: a combination of single-crystal three-dimensional electron diffraction and powder X-ray diffraction.

The solid-state structure of star-shaped 2,4,6-tris{(E)-2-[4-(dimethylamino)-phenyl]ethenyl}-1,3,5-triazine is determined from a powder sample by exploiting the respective strengths of single-crystal three-dimensional electron diffraction and powder X-ray diffraction data. The unit-cell parameters were determined from single crystal electron diffraction data. Using this information, the powder X-ray diffraction data were indexed, and the crystal structure was determined from the powder diffraction profile. The compound crystallizes in a noncentrosymmetric space group, P212121. The molecular conformation in the crystal structure was used to calculate the molecular dipole moment of 3.22 Debye, which enables the material to show nonlinear optical effects.

Molybdenum Oxide Nitrides of the Mo2(O,N,□)5 Type: On the Way to Mo2O5.

Blue-colored molybdenum oxide nitrides of the Mo2(O,N,□)5 type were synthesized by direct nitridation of commercially available molybdenum trioxide with a mixture of gaseous ammonia and oxygen. Chemical composition, crystal structure, and stability of the obtained and hitherto unknown compounds are studied extensively. The average oxidation state of +5 for molybdenum is proven by Mo K near-edge X-ray absorption spectroscopy; the magnetic behavior is in agreement with compounds exhibiting MoVO6 units. The new materials are stable up to ∼773 K in an inert gas atmosphere. At higher temperatures, decomposition is observed. X-ray and neutron powder diffraction, electron diffraction, and high-resolution transmission electron microscopy reveal the structure to be related to VNb9O24.9-type phases, however, with severe disorder hampering full structure determination. Still, the results demonstrate the possibility of a future synthesis of the potential binary oxide Mo2O5. On the basis of these findings, a tentative suggestion on the crystal structure of the potential compound Mo2O5, backed by electronic-structure and phonon calculations from first principles, is given.

Haloperoxidase Mimicry by CeO2-x Nanorods Combats Biofouling.

CeO2-x nanorods are functional mimics of natural haloperoxidases. They catalyze the oxidative bromination of phenol red to bromophenol blue and of natural signaling molecules involved in bacterial quorum sensing. Laboratory and field tests with paint formulations containing 2 wt% of CeO2-x nanorods show a reduction in biofouling comparable to Cu2 O, the most typical biocidal pigment.