A Pillar[5]arene-Containing Metal-Organic Framework for Rapid and Highly Capable Adsorption of a Mustard Gas Simulant.

Mustard gas causes irreversible damage upon inhalation or contact with the human body. Consequently, the development of adsorbents for effective interception of mustard gas at low concentrations and high flow rates is an urgent necessity. Here we report a stable porous pillar[5]arene-containing metal-organic framework (MOF) based on zirconium (EtP5-Zr-scu), demonstrating that embedding pillar[5]arene units in MOFs can provide specific binding sites for efficient adsorption of a mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES). EtP5-Zr-scu achieves a higher capacity and more rapid adsorption compared to its counterpart without embedded pillar[5]arene units (H4tcpt-Zr-scu) and perethylated pillar[5]arene (EtP5) alone. Single crystal X-ray diffraction and solid-state nuclear magnetic resonance reveal that the enhanced performance of EtP5-Zr-scu is derived from the host-guest complexation between CEES and pillar[5]arene moieties. Moreover, breakthrough experiments confirmed that the interception performance of EtP5-Zr-scu against CEES (800 ppm, 120 mL/min) was significantly improved (566 min/g) compared with H4tcpt-Zr-scu (353 min/g) and EtP5 (0.873 min/g), attributed to the integration of open channels with specific recognition sites. This work marks a significant advancement in the development of macrocycle-incorporated crystalline framework materials with recognition sites for the efficient capture of guest molecules.

Heat-Resistant Carbon-Coated Potassium Magnesium Hexacyanoferrate Nanoplates for High-Performance Potassium-Ion Batteries.

Metal hexacyanoferrates (HCFs) are regarded as promising cathode materials for potassium-ion batteries (PIBs) on account of their low cost and high energy density. However, the difficult-to-remove [Fe(CN)6] vacancies and crystal water lead to structural instability and capacity deterioration as well as the stereotype of poor thermostability of conventional HCFs. Herein, we report (100) face-oriented potassium magnesium hexacyanoferrate (KMgHCF) nanoplates with low [Fe(CN)6] vacancies and high crystallinity, enabling thermostability up to 550 °C, high-temperature carbon coating and crystal water elimination. The as-obtained KMgHCF/C nanoplates exhibit superior potassium storage properties, including a large reversible capacity of 84.6 mAh g-1, a high voltage plateau of 3.87 V, excellent long-term cycling performance over 15000 cycles and high rate capability at 5 A g-1. The unprecedented cycling stability of KMgHCF/C is attributed to the synergistic effect of a highly reversible two-phase reaction, low [Fe(CN)6] vacancies and no crystal water, a specially exposed steady (100) surface, and a protective carbon coating. This work provides a new material selection and modification strategy for the practical application of HCFs in PIBs.

Three-Dimensional Crystalline Organic Framework Stabilized by Molecular Mortise-and-Tenon Jointing.

Three-dimensional (3D) crystalline organic frameworks with complex topologies, high surface area, and low densities afford a variety of application prospects. However, the design and construction of these frameworks have been largely limited to systems containing polyhedron-shaped building blocks or those relying on component interpenetration. Here, we report the synthesis of a 3D crystalline organic framework based on molecular mortise-and-tenon jointing. This new material takes advantage of tetra(4-pyridylphenyl)ethylene and chlorinated bis(benzodioxaborole)benzene as building blocks and is driven by dative B-N bonds. A single-crystal X-ray diffraction analysis of the framework reveals the presence of two-dimensional (2D) layers with helical channels that are formed presumably during the boron-nitrogen coordination process. The protrusion of dichlorobenzene units from the upper and lower surfaces of the 2D layers facilitates the key mortise-and-tenon connections. These connections enable the interlocking of adjacent layers and the stabilization of an overall 3D framework. The resulting framework is endowed with high porosity and attractive mechanical properties, rendering it potentially suitable for the removal of impurities from acetylene.

Efficient Purification of 2,6-Lutidine by Nonporous Adaptive Crystals of Pillararenes.

2,6-Lutidine (2,6-LT) is a very important raw material in the chemical industry, but the impurities of 3-picoline (3-PC) and 4-picoline (4-PC) existing in 2,6-LT seriously affect its quality. Considering different molecular sizes of these three compounds, herein, we exploit nonporous adaptive crystals (NACs) of pillararenes as purifying agents for removal of 3-PC and 4-PC in 2,6-LT. We find that per-ethylated pillar[5]arene (EtP5) can selectively adsorb 3-PC and 4-PC, while negligible capture of 2,6-LT is observed, resulting in improvement of the purity of 2,6-LT up to 94.9%. Single-crystal structures indicate that the excellent selectivity originates from the size match and complexation stability differences among different host/guest pairs. After purification, NACs of EtP5 can be easily regenerated and used in the next run without a significant performance degradation.

Mechanically interlocked polymers based on rotaxanes.

The nature of mechanically interlocked molecules (MIMs) has continued to encourage researchers to design and construct a variety of high-performance materials. Introducing mechanically interlocked structures into polymers has led to novel polymeric materials, called mechanically interlocked polymers (MIPs). Rotaxane-based MIPs are an important class, where the mechanically interlocked characteristic retains a high degree of structural freedom and mobility of their components, such as the rotation and sliding motions of rotaxane units. Therefore, these MIP materials are known to possess a unique set of properties, including mechanical robustness, adaptability and responsiveness, which endow them with potential applications in many emerging fields, such as protective materials, intelligent actuators, and mechanisorption. In this review, we outline the synthetic strategies, structure-property relationships, and application explorations of various polyrotaxanes, including linear polyrotaxanes, polyrotaxane networks, and rotaxane dendrimers.

Construction of pillar[4]arene[1]quinone-1,10-dibromodecane pseudorotaxanes in solution and in the solid state.

We report novel pseudorotaxanes based on the complexation between pillar[4]arene[1]quinone and 1,10-dibromodecane. The complexation is found to have a 1:1 host-guest complexation stoichiometry in chloroform but a 2:1 host-guest complexation stoichiometry in the solid state. From single crystal X-ray diffraction, the linear guest molecules thread into cyclic pillar[4]arene[1]quinone host molecules in the solid state, stabilized by CH∙∙∙π interactions and hydrogen bonds. The bromine atoms at the periphery of the guest molecule provide convenience for the further capping of the pseudorotaxanes to construct rotaxanes.

Separation of 2-Chloropyridine/3-Chloropyridine by Nonporous Adaptive Crystals of Pillararenes with Different Substituents and Cavity Sizes.

Two monochloropyridine isomers, 2-chloropyridine (2-CP) and 3-chloropyridine (3-CP), are in need of a more effective separation method besides rectification. Herein we offer a facile and energy-saving adsorptive separation strategy using nonporous adaptive crystals of perethylated pillar[5]arene (EtP5), perethylated pillar[6]arene (EtP6), perbromoethylated pillar[5]arene (BrP5), and perbromoethylated pillar[6]arene (BrP6), which possess different cavity sizes and substituents and have never been employed in the separation of single-substituted heterocyclic aromatic compounds. BrP6 crystals show a marked preference for 2-CP in the equimolar mixture of 2-CP and 3-CP, affording it with 96.4% purity. Single crystal diffraction experiments demonstrate that BrP6 has stronger host-guest interactions with 2-CP than 3-CP. The cycling experiments demonstrate that BrP6 crystals can be used at least five times without losing their adsorption selectivity or capacity.

Vapochromic crystals: understanding vapochromism from the perspective of crystal engineering.

Vapochromic materials, which undergo colour and/or emission changes upon exposure to certain vapours or gases, have received increasing attention recently because of their wide range of applications in, e.g., chemical sensors, light-emitting diodes, and environmental monitors. Vapochromic crystals, as a specific kind of vapochromic materials, can be investigated from the perspective of crystal engineering to understand the mechanism of vapochromism. Moreover, understanding the vapochromism mechanism will be beneficial to design and prepare task-specific vapochromic crystals as one kind of low-cost 'electronic nose' to detect toxic gases or volatile organic compounds. This review provides important information in a broad scientific context to develop new vapochromic materials, which covers organometallic or coordination complexes and organic crystals, as well as the different mechanisms of the related vapochromic behaviour. In addition, recent examples of supramolecular vapochromic crystals and metal-organic-framework (MOFs) vapochromic crystals are introduced.