Atomic observation and structural evolution of covalent organic framework rotamers.

Dynamic 3D covalent organic frameworks (COFs) have shown concerted structural transformation and adaptive gas adsorption due to the conformational diversity of organic linkers. However, the isolation and observation of COF rotamers constitute undergoing challenges due to their comparable free energy and subtle rotational energy barrier. Here, we report the atomic-level observation and structural evolution of COF rotamers by cryo-3D electron diffraction and synchrotron powder X-ray diffraction. Specifically, we optimize the crystallinity and morphology of COF-320 to manifest its coherent dynamic responses upon adaptive inclusion of guest molecules. We observe a significant crystal expansion of 29 vol% upon hydration and a giant swelling with volume change up to 78 vol% upon solvation. We record the structural evolution from a non-porous contracted phase to two narrow-pore intermediate phases and the fully opened expanded phase using n-butane as a stabilizing probe at ambient conditions. We uncover the rotational freedom of biphenylene giving rise to significant conformational changes on the diimine motifs from synclinal to syn-periplanar and anticlinal rotamers. We illustrate the 10-fold increment of pore volumes and 100% enhancement of methane uptake capacity of COF-320 at 100 bar and 298 K. The present findings shed light on the design of smarter organic porous materials to maximize host-guest interaction and boost gas uptake capacity through progressive structural transformation.

De Novo Design and Facile Synthesis of Highly Crystalline 2D Conductive Metal-Organic Frameworks: A "Rotor-Stator" Strategy.

Two-dimensional conductive metal-organic frameworks (2D c-MOFs), which feature high electrical conductivity and large charge carrier mobility, hold great promise in electronics and optoelectronics. Nevertheless, the limited solubility of commonly used planar ligands inevitably brings challenges in synthesis and purification and causes laborious coordination conditions for screening. Moreover, most reported 2D c-MOFs are polycrystalline powders with relatively low crystallinity and irregular morphology, hindering the unveiling of the detailed structure-function relationship. Herein, we developed a "rotor-stator" molecular design strategy to construct 2D c-MOFs using a delicately designed nonplanar biscarbazole ligand (8OH-DCB). Benefiting from the special "rotor-stator" structure of the ligand, crystals of Cu-DCB-MOF were successfully prepared, allowing for the precise determination of their crystal structure. Interestingly, the crystals of Cu-DCB-MOF can be obtained in various organic solvents, indicating excellent solvent compatibility. The versatility of the "rotor-stator" molecular design strategy was further demonstrated by another two new ligands with a "rotor-stator" structure, and afford corresponding 2D c-MOF crystals (Cu-DCBT-MOF and Cu-DCBBT-MOF). The current work presents a facile approach toward the rational design and direct construction of highly crystalline 2D c-MOFs using nonplanar ligands.

Cinquefoil Knot Possessing Dynamic and Tunable Metal Coordination.

While the majority of knots are made from the metal-template approach, the use of entangled, constrained knotted loops to modulate the coordination of the metal ions remains inadequately elucidated. Here, we report on the coordination chemistry of a 140-atom-long cinquefoil knotted strand comprising five tridentate and five bidentate chelating vacancies. The knotted loop is prepared through the self-assembly of asymmetric "3 + 2" dentate ligands with copper(II) ions that favor five-coordination geometry. The formation of the copper(II) pentameric helicate is confirmed by X-ray crystallography, while the corresponding copper(II) knot is characterized by XPS and LR-/HR ESI-MS. Upon removal of the original template, the knotted ligand facilitates zinc(II) ions, which typically form four- or six-coordination geometries, resulting in the formation of an otherwise inaccessible zinc(II) metallic knot with coordinatively unsaturated metal centers. The coordination numbers and geometries of the zinc(II) cations are undoubtedly determined by X-ray crystallography. Despite the kinetically labile nature and high reversibility of the zinc(II) complex preventing the detection of 5-to-6 coordination equilibrium in solution, the effects on metal-ion coordination induced by knotting hold promise for fine-tuning the coordination of metal complexes.

Tricoordinated Single-Atom Cobalt in Zeolite Boosting Propane Dehydrogenation.

Propane dehydrogenation (PDH) reaction has emerged as one of the most promising propylene production routes due to its high selectivity for propylene and good economic benefits. However, the commercial PDH processes usually rely on expensive platinum-based and poisonous chromium oxide based catalysts. The exploration of cost-effective and ecofriendly PDH catalysts with excellent catalytic activity, propylene selectivity, and stability is of great significance yet remains challenging. Here, we discovered a new active center, i.e., an unsaturated tricoordinated cobalt unit (≡Si-O)CoO(O-Mo) in a molybdenum-doped silicalite-1 zeolite, which afforded an unprecedentedly high propylene formation rate of 22.6 molC3H6 gCo-1 h-1 and apparent rate coefficient of 130 molC3H6 gCo-1 h-1 bar-1 with >99% of propylene selectivity at 550 °C. Such activity is nearly one magnitude higher than that of previously reported Co-based catalysts in which cobalt atoms are commonly tetracoordinated, and even superior to that of most of Pt-based catalysts under similar operating conditions. Density functional theory calculations combined with the state-of-the-art characterizations unravel the role of the unsaturated tricoordinated Co unit in facilitating the C-H bond-breaking of propane and propylene desorption. The present work opens new opportunities for future large-scale industrial PDH production based on inexpensive non-noble metal catalysts.

Observation of Chiral Channels in Helical Covalent Organic Frameworks.

Unraveling the mechanism of chirality transfer across length scales is crucial to the rational development of functional materials with hierarchical chirality. The key obstacle is the lack of structural information, especially at the mesoscopic level. We report herein the structural identification of helical covalent organic frameworks (heliCOFs) with hierarchical chirality, which integrate molecular chirality, channel chirality, and morphology chirality into one crystalline entity. Specifically, benefiting from the highly ordered structure of heliCOFs, the existence of chiral channels at the mesoscopic level has been confirmed by electron crystallography, and the handedness of these chiral channels has been directly determined through the stereopair imaging technique. Accordingly, the chirality transfer in heliCOFs from microscopic to macroscopic levels could be rationalized with a layer-rotating model that has been supported by both crystal structure analysis and theoretical calculations. Observation of chiral channels in heliCOFs not only provides unprecedented data for the understanding of the chirality transfer process but also sheds new light on the rational construction of highly ordered polymeric materials with hierarchical chirality.

A Stable Extra-Large Pore and High-Silica Zeolite Derived from Ge-Rich Precursor.

A multidimensional extra-large pore zeolite with highly hydrothermal stability, denoted as -IRT-HS, has been developed successfully, starting from Ge-rich germanosilicate precursor hydrothermally directed by a small and commercially available piperidinium-type organic structure-directing agent (OSDA). -IRT-HS, with the supermicropores, is structurally analogues to 28-membered ring -IRT topology as confirmed by various spectroscopic techniques. And it is the high-silica (Si/Ge=58) zeolite with the largest pore size as well. Notably, using acid-washed as-made Ge-rich -IRT precursor as the silicon source is crucial to restore partially collapsed structure into a stable framework by OSDA-assisted recrystallization. The calcined -IRT-HS maintains a high crystallinity, even when stored in a humid environment for extended periods or directly exposed to water. Additionally, high silica Al-containing analogue is also readily synthesized, serving as an active solid-acid catalyst in 1,3,5-triisopropylbenzene cracking reaction, yielding an impressive initial conversion up to 76.1 % much higher than conventional large-pore Beta zeolite (30.4 %). This work will pave the way for the designed synthesis of targeted high-silica zeolites with stable and extra-large pore frameworks, mimicking the structures of existing Ge-rich counterparts.

Structural analysis of nanocrystals by pair distribution function combining electron diffraction with crystal tilting.

As an important characterization method, pair distribution function (PDF) has been extensively used in structural analysis of nanomaterials, providing key insights into the degree of crystallinity, atomic structure, local disorder etc. The collection of scattering signals with good statistics is necessary for a reliable structural analysis. However, current conventional electron diffraction experiments using PDF (ePDF) are limited in their ability to acquire continuous diffraction rings for large nanoparticles. Herein, a new method - tilt-ePDF - is proposed to improve the data quality and compatibility of ePDF by a combination of electron diffraction and specimen tilting. In the present work, a tilt-series of electron diffraction patterns was collected from gold nanoparticles with three different sizes and a standard sample polycrystalline aluminium film for ePDF analysis. The results show that tilt-ePDF can not only enhance the continuity of diffraction rings, but can also improve the signal-to-noise ratio in the high scattering angle range. As a result, compared with conventional ePDF data, tilt-ePDF data provide structure parameters with a better accuracy and lower residual factors in the refinement against the crystal structure. This method provides a new way of utilizing ePDF to obtain accurate local structure information from nanoparticles.

Chirality Determination of Nanocrystals by Electron Crystallography.

Chirality is a common phenomenon in nature and plays an important role in the properties of matter. The rational synthesis of chiral compounds and exploration of their applications in various fields require an unambiguous determination of their handedness. However, in many cases, determinations of the chiral crystal structure and chiral morphology have been a challenging task due to the lack of proper characterization methods, especially for nanosized crystals. Therefore, it is crucial to develop novel and efficient characterization methods. Owing to the strong interactions between matter and electrons, electron crystallography has become a powerful tool for structural analysis of nanomaterials. In recent years, methods based on electron crystallography, such as high-resolution electron microscopy imaging and electron diffraction, have been developed to unravel the chirality of nanomaterials. This brings new opportunities to the design, synthesis, and applications of versatile chiral nanomaterials. In this perspective, we summarize the recent methodology developments and ongoing research of electron crystallography for chiral structure and morphology determination of nanocrystals, including inorganic and organic materials, as well as highlight the potential and further improvement of these methods in the future.