Compact Coupled Graphene and Porous Polyaryltriazine‐Derived Frameworks as High Performance Cathodes for Lithium‐Ion Batteries

It is highly desirable to develop electroactive organic materials and their derivatives as green alternatives of cathodes for sustainable and cost‐effective lithium‐ion batteries (LIBs) in energy storage fields. Herein, compact two‐dimensional coupled graphene and porous polyaryltriazine‐derived frameworks with tailormade pore structures are fabricated by using various molecular building blocks under ionothermal conditions. The porous nanosheets display nanoscale thickness, high specific surface area, and strong coupling of electroactive polyaryltriazine‐derived frameworks with graphene. All these features make it possible to efficiently depress the dissolution of redox moieties in electrolytes and to boost the electrical conductivity of whole electrode. When employed as a cathode in LIBs, the two‐dimensional porous nanosheets exhibit outstanding cycle stability of 395 mAh g^?1 at 5 A g^?1 for more than 5100 cycles and excellent rate capability of 135 mAh g^?1 at a high current density of 15 A g^?1.     

Electroactive Organic Building Blocks for the Chemical Design of Functional Porous Frameworks (MOFs and COFs) in Electronics

Electroactive organic molecules have received a lot of attention in the field of electronics because of their fascinating electronic properties, easy functionalization and potential low cost towards their implementation in electronic devices. In recent years, electroactive organic molecules have also emerged as promising building blocks for the design and construction of crystalline porous frameworks such as metal–organic frameworks (MOFs) and covalent-organic frameworks (COFs) for applications in electronics. Such porous materials present certain additional advantages such as, for example, an immense structural and functional versatility, combination of porosity with multiple electronic properties and the possibility of tuning their physical properties by post-synthetic modifications. In this Review, we summarize the main electroactive organic building blocks used in the past few years for the design and construction of functional porous materials (MOFs and COFs) for electronics with special emphasis on their electronic structure and function relationships. The different building blocks have been classified based on the electronic nature and main function of the resulting porous frameworks. The design and synthesis of novel electroactive organic molecules is encouraged towards the construction of functional porous frameworks exhibiting new functions and applications in electronics.     

Ultrathin 2D Covalent Organic Framework Film Fabricated via Langmuir-Blodgett Method with a “Two-in-One” Type Monomer

In recent years, covalent organic frameworks(COFs) are evolving as a novel kind of porous materials for catalysis and molecular separation, gas adsorption, etc. Various functional building blocks have been explored to tune the pore channels, including the pore size and structures. In this article, a new terphenyl(TP) based COF(TP-COF) was developed via a “two-in-one” strategy by using a symmetric A₂B₂monomer, i.e., 4,4'-diamino-2',5'-diformyl-1,1':4',1'-terphenyl(DADFTP). The pore size of TP-COF was only 0.99 nm by shortening the arm length of the DADFTP monomer. Freestanding, continuous and ultrathin COF films could be facilely prepared at the air-liquid interface through the modified Langmuir-Blodgett(LB) method. TP-COF films exhibited high rejection of over 90% for dyes removal.     

Topology-Templated Synthesis of Crystalline Porous Covalent Organic Frameworks

A strategy is presented for the synthesis of crystalline porous covalent organic frameworks via topology-templated polymerization. The template is based on imine-linked frameworks and their (001) facets seed the C=C bond formation reaction to constitute 2D sp² carbon-conjugated frameworks. This strategy is applicable to templates with different topologies, enables designed synthesis of frameworks that cannot be prepared via direct polymerization, and creates a series of sp² carbon frameworks with tetragonal, hexagonal, and kagome topologies. The sp² carbon frameworks are highly luminescent even in the solid state and exhibit topology-dependent π transmission and exciton migration; these key fundamental π functions are unique to sp² carbon-conjugated frameworks and cannot be accessible by imine-linked frameworks, amorphous analogues, and 1D conjugated polymers. These results demonstrate an unprecedented strategy for structural and functional designs of covalent organic frameworks.     

Topology‐Templated Synthesis of Crystalline Porous Covalent Organic Frameworks

A strategy is presented for the synthesis of crystalline porous covalent organic frameworks via topology‐templated polymerization. The template is based on imine‐linked frameworks and their (001) facets seed the C=C bond formation reaction to constitute 2D sp² carbon‐conjugated frameworks. This strategy is applicable to templates with different topologies, enables designed synthesis of frameworks that cannot be prepared via direct polymerization, and creates a series of sp² carbon frameworks with tetragonal, hexagonal, and kagome topologies. The sp² carbon frameworks are highly luminescent even in the solid state and exhibit topology‐dependent π transmission and exciton migration; these key fundamental π functions are unique to sp² carbon‐conjugated frameworks and cannot be accessible by imine‐linked frameworks, amorphous analogues, and 1D conjugated polymers. These results demonstrate an unprecedented strategy for structural and functional designs of covalent organic frameworks.     

Effect of Building Block Transformation in Covalent Triazine-Based Frameworks for Enhanced CO2 Uptake and Metal-Free Heterogeneous Catalysis

Covalent triazine frameworks (CTFs) have provided a unique platform in functional material design for a wide range of applications. This work reports a series of new CTFs with two new heteroaromatic building blocks (pyrazole and isoxazole groups) through a building-block transformation approach aiming for carbon capture and storage (CCS) and metal-free catalysis. The CTFs were synthesized from their respective building blocks [(4,4′-(1H-pyrazole-3,5-diyl)dibenzonitrile (pyz) and 4,4′-(isoxazole-3,5-diyl)dibenzonitrile (isox))] under ionothermal conditions using ZnCl₂. Both of the building blocks were designed by an organic transformation of an acetylacetone containing dinitrile linker to pyrazole and isoxazole groups, respectively. Due to this organic transformation, (i) linker aromatization, (ii) higher surface areas and nitrogen contents, (iii) higher aromaticity, and (iv) higher surface basicity was achieved. Due to these enhanced properties, CTFs were explored for CO₂ uptake and metal-free heterogeneous catalysis. Among all, the isox-CTF, synthesized at 400 °C, showed the highest CO₂ uptake (4.92 mmol g⁻¹ at 273 K and 2.98 mmol g⁻¹ at 298 K at 1 bar). Remarkably, these CTFs showed excellent metal-free catalytic activity for the aerobic oxidation of benzylamine at mild reaction conditions. On studying the properties of the CTFs, it was observed that organic transformations and ligand aromatization of the materials are crucial factor to tune the important parameters that influence the CO₂ uptake and the catalytic activity. Overall, this work highlights the substantial effect of designing new CTF materials by building-block organic transformations resulting in better properties for CCS applications and heterogeneous catalysis.     

Fortified Coiled Coils: Enhancing Mechanical Stability with Lactam or Metal Staples

Coiled coils (CCs) are powerful supramolecular building blocks for biomimetic materials, increasingly used for their mechanical properties. Here, we introduce helix‐inducing macrocyclic constraints, so‐called staples, to tune thermodynamic and mechanical stability of CCs. We show that thermodynamic stabilization of CCs against helix uncoiling primarily depends on the number of staples, whereas staple positioning controls CC mechanical stability. Inserting a covalent lactam staple at one key force application point significantly increases the barrier to force‐induced CC dissociation and reduces structural deformity. A reversible His‐Ni²⁺‐His metal staple also increases CC stability, but ruptures upon mechanical loading to allow helix uncoiling. Staple type, position and number are key design parameters in using helical macrocyclic templates for fine‐tuning CC properties in emerging biomaterials.     

Clicked Isoreticular Metal–Organic Frameworks and Their High Performance in the Selective Capture and Separation of Large Organic Molecules

Three highly porous metal–organic frameworks (MOFs) with a uniform rht‐type topological network but hierarchical pores were successfully constructed by the assembly of triazole‐containing dendritic hexacarboxylate ligands with Zn^II ions. These transparent MOF crystals present gradually increasing pore sizes upon extension of the length of the organic backbone, as clearly identified by structural analysis and gas‐adsorption experiments. The inherent accessibility of the pores to large molecules endows these materials with unique properties for the uptake of large guest molecules. The visible selective adsorption of dye molecules makes these MOFs highly promising porous materials for pore‐size‐dependent large‐molecule capture and separation.     

A π-Conjugated,Covalent Phosphinine Framework

Structural modularity of polymer frameworks is a key advantage of covalent organic polymers, however, only C, N, O, Si, and S have found their way into their building blocks so far. Here, the toolbox available to polymer and materials chemists is expanded by one additional nonmetal, phosphorus. Starting with a building block that contains a λ⁵-phosphinine (C₅P) moiety, a number of polymerization protocols are evaluated, finally obtaining a π-conjugated, covalent phosphinine-based framework (CPF-1) through Suzuki–Miyaura coupling. CPF-1 is a weakly porous polymer glass (72.4 m² g⁻¹ BET at 77 K) with green fluorescence (λ_max=546 nm) and extremely high thermal stability. The polymer catalyzes hydrogen evolution from water under UV and visible light irradiation without the need for additional co-catalyst at a rate of 33.3 μmol h⁻¹ g⁻¹. These results demonstrate for the first time the incorporation of the phosphinine motif into a complex polymer framework. Phosphinine-based frameworks show promising electronic and optical properties, which might spark future interest in their applications in light-emitting devices and heterogeneous catalysis.     

Tetrathiafulvalene-based covalent organic frameworks for ultrahigh iodine capture

To safeguard the development of nuclear energy, practical techniques for capture and storage of radioiodine are of critical importance but remain a significant challenge. Here we report the synergistic effect of physical and chemical adsorption of iodine in tetrathiafulvalene-based covalent organic frameworks (COFs), which can markedly improve both iodine adsorption capacity and adsorption kinetics due to their strong interaction. These functionalized architectures are designed to have high specific surface areas (up to 2359 m² g⁻¹) for efficient physisorption of iodine, and abundant tetrathiafulvalene functional groups for strong chemisorption of iodine. We demonstrate that these frameworks achieve excellent iodine adsorption capacity (up to 8.19 g g⁻¹), which is much higher than those of other materials reported so far, including silver-doped adsorbents, inorganic porous materials, metal–organic frameworks, porous organic frameworks, and other COFs. Furthermore, a combined theoretical and experimental study, including DFT calculations, electron paramagnetic resonance spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy, reveals the strong chemical interaction between iodine and the frameworks of the materials. Our study thus opens an avenue to construct functional COFs for a critical environment-related application.

The synergistic effect of physical and chemical adsorption of iodine in tetrathiafulvalene-based covalent organic frameworks (COFs) has been explored. The iodine adsorption capacity of these materials is higher than other materials reported so far.     

Accurate van der Waals force field for gas adsorption in porous materials

An accurate van der Waals force field (VDW FF) was derived from highly precise quantum mechanical (QM) calculations. Small molecular clusters were used to explore van der Waals interactions between gas molecules and porous materials. The parameters of the accurate van der Waals force field were determined by QM calculations. To validate the force field, the prediction results from the VDW FF were compared with standard FFs, such as UFF, Dreiding, Pcff, and Compass. The results from the VDW FF were in excellent agreement with the experimental measurements. This force field can be applied to the prediction of the gas density (H₂, CO₂, C₂H₄, CH₄, N₂, O₂) and adsorption performance inside porous materials, such as covalent organic frameworks (COFs), zeolites and metal organic frameworks (MOFs), consisting of H, B, N, C, O, S, Si, Al, Zn, Mg, Ni, and Co. This work provides a solid basis for studying gas adsorption in porous materials. © 2017 Wiley Periodicals, Inc.     

Deaminative meta-C–H alkylation by ruthenium(ii) catalysis

Precise structural modifications of amino acids are of importance to tune biological properties or modify therapeutical capabilities relevant to drug discovery. Herein, we report a ruthenium-catalyzed meta-C–H deaminative alkylation with easily accessible amino acid-derived Katritzky pyridinium salts. Likewise, remote C–H benzylations were accomplished with high levels of chemoselectivity and remarkable functional group tolerance. The meta-C–H activation approach combined with our deaminative strategy represents a rare example of selectively converting C(sp³)–N bonds into C(sp³)–C(sp²) bonds.

Precise structural modifications of amino acids are of importance to tune biological properties or modify therapeutical capabilities relevant to drug discovery.     

A Mixed Molecular Building Block Strategy for the Design of Nested Polyhedron Metal–Organic Frameworks

A mixed molecular building block (MBB) strategy for the synthesis of double‐walled cage‐based porous metal–organic frameworks (MOFs) is presented. By means of this method, two isostructural porous MOFs built from unprecedented double‐walled metal–organic octahedron were obtained by introducing two size‐matching C₃‐symmetric molecular building blocks with different rigidities. With their unique framework structures, these MOFs provide, to the best of our knowledge, the first examples of double‐walled octahedron‐based MOFs.     

New synthetic strategies and disconnections in the synthesis of liquid crystals enabled by photoredox cross-coupling reactions

In this letter we describe the application of metallaphotoredox cross-electrophile couplings to the synthesis of liquid crystals using dual nickel and iridium catalysis. Given the proliferation of aryl and alkyl bromides in liquid crystal research we consider that the silyl-radical mediated cross-coupling of alkyl bromide with an aryl bromide (to afford a direct alkyl–aryl bond) will become an extremely powerful tool in the synthesis of liquid crystalline materials, and we use this to synthesise several well-known materials (PCH32, 5CB, CB7CB and CB15) in a single synthetic step from inexpensive and commercially available building blocks. The metallaphotoredox decarboxylative sp³–sp² cross-coupling of an aryl bromide with an alkyl carboxylic acid provides a complimentary method to form alkyl–aryl bonds, and we use this to successfully prepare trans PCH5 in a single synthetic step from commercially available building blocks. We also prepare novel methylene-linked materials in a single synthetic step, one of which exhibit the topical TB phase.     

Highly Efficient Enrichment of Volatile Iodine by Charged Porous Aromatic Frameworks with Three Sorption Sites

The targeted synthesis of a series of novel charged porous aromatic frameworks (PAFs) is reported. The compounds PAF‐23, PAF‐24, and PAF‐25 are built up by a tetrahedral building unit, lithium tetrakis(4‐iodophenyl)borate (LTIPB), and different alkyne monomers as linkers by a Sonogashira–Hagihara coupling reaction. They possess excellent adsorption properties to organic molecules owing to their “breathing” dynamic frameworks. As these PAF materials assemble three effective sorption sites, namely the ion bond, phenyl ring, and triple bond together, they exhibit high affinity and capacity for iodine molecules. To the best of our knowledge, these PAF materials give the highest adsorption values among all porous materials (zeolites, metal–organic frameworks, and porous organic frameworks) reported to date.     

Graphynes and graphdyines

In this paper, the experimental and theoretical results that may give an insight into the current status and possible prospects of the family of (sp¹ + sp²) hybridized carbon allotropes: graphynes (GYs) and graphdiynes (GDYs), are reviewed. These allotropes, which can form a rich variety of 0D-3D forms and demonstrate a set of distinguished properties, have attracted now increased attention and research interest as promising materials, which can compete in various potential applications with “conventional” sp² carbon systems such as fullerenes, nanotubes or graphene and meet the increasing requirements to carbon-based nanomaterials.It can be seen from the increasing number of publications in the last five years that the interest in GYs and GDYs rapidly grows, and a lot of new results have been obtained today. For example, a set of 0D-3D forms of GYs and GDYs have been successfully synthesized and (or) predicted theoretically, and their key properties (structural, mechanical, electronic etc.) have been measured or estimated from ab initio calculations. This gives a strong impetus to further progress in applications of GYs and GDYs as materials for nanoelectronics, energy storage, as anode materials in batteries, as membranes for facilitating selective gas separation etc. All these efforts promote the expansion of the palette of promising carbon materials and accelerate the development of modern carbon-based technologies.     

Viologen derivatives with extended π-conjugation structures: From supra-/molecular building blocks to organic porous materials

Recently, increasing attention has been paid on extending the π-conjugation structures of viologens (1,1′-disubstituted-4,4′-bipyridylium salts) by incorporating planar aromatic units into the bipyridinium backbones. Various viologen derivatives with extended π-conjugation structures have been synthesized, including the N-termini aromatic substituted viologens, the extended π-conjugated viologens (denoted as ECVs) as well as the π-conjugated oligomeric viologens (denoted as COVs). These compounds typically exhibit interesting properties distinguished from those of an isolated viologen unit, which make them as new class of electron deficient supra-/molecular building blocks in supramolecular chemistry and materials science. In this review, we would like to highlight the recent advances of viologen derivatives with extended π-conjugation structures in versatile applications ranging from electrochromic and energy storage materials, the ECV/COV-based supramolecular self-assembly systems including the linear supramolecular polymers and 2D/3D supramolecular organic frameworks (SOFs), to the viologen-based covalent organic frameworks (COFs)/networks. We hope this review will serve as an in-time summary worthy of referring, more importantly, to provide inspiration in the rational design of novel molecules with unexplored properties and functions.     

Deformation Behavior of Three-Dimensional Carbon Structures Under Hydrostatic Compression

The paper presents the results of numerical simulation aimed at studying the deformation behavior of carbon structures containing carbon atoms with various coordination numbers and, consequently, various electronic configurations and properties. Namely, the method of molecular dynamics was used to study the deformation behavior of two different structures of crumpled graphene (sp²-material formed by graphene flakes bonded by Van der Waals forces) and carbon diamond-like phases (rigid sp³-structures) under hydrostatic compression. Stress-strain curves have been obtained, structural features have been shown to affect mechanical properties of three-dimensional carbon structures.     

Covalent Organic Frameworks and Cage Compounds: Design and Applications of Polymeric and Discrete Organic Scaffolds

Porous organic materials are an emerging class of functional nanostructures with unprecedented properties. Dynamic covalent assembly of small organic building blocks under thermodynamic control is utilized for the intriguingly simple formation of complex molecular architectures in one‐pot procedures. In this Review, we aim to analyze the basic design principles that govern the formation of either covalent organic frameworks as crystalline porous polymers or covalent organic cage compounds as shape‐persistent molecular objects. Common synthetic procedures and characterization techniques will be discussed as well as more advanced strategies such as postsynthetic modification or self‐sorting. When appropriate, comparisons are drawn between polymeric frameworks and discrete organic cages in terms of their underlying properties. Furthermore, we highlight the potential of these materials for applications ranging from gas storage to catalysis and organic electronics.     

Ferrocene-based hypercrosslinked polymers derived from phenolic polycondensation with unexpected H2 adsorption capacity

Metal-doped porous organic polymers often display unique properties for applications in gas uptake owing to the incorporation of the metal elements in the polymer networks. In this study, a series of novel ferrocene-based hypercrosslinked polymers were prepared by phenolic polycondensation (Fc-PR-HCPs). To generate the hypercrosslinked polymers, 1,1′-ferrocenedicarboxaldehyde (Fc(CHO)₂) and bisphenol A (BPA) were used as the building blocks. The maximum value of BET and micropore surface area is determined to be 1111.4 and 487.4 m²/g for Fc-PR-HCP3. A significant H₂ adsorption capacity of 3.11 wt% was achieved for Fc-PR-HCP3 at 77 K/1.0 bar, which was noted to be higher than the porous organic polymers with even higher BET surface area value. The high micropore surface area value and the adsorption sites (aromatic rings and metal ion-active sites) provided by two building blocks were used to explain the significant H₂ adsorption capacity successfully. Overall, the findings from this study indicate that Fc-PR-HCPs highlighted prospective applications in the field of H₂ capture.