Organic Building Blocks Research Articles

Room-Temperature Preparation of Covalent Organic Framework Membrane for Nanofiltration.

The uniquely tunable nature of covalent organic frameworks (COFs), whose pore size and stability can be controlled by choosing diverse organic building blocks and linkage types, makes COFs potential candidates for the membrane separation. Therefore, the preparation of membranes with effective separation efficiency based on COFs has aroused great interest among researchers. Although solvothermal approach has been the most popular method for the preparation of COF membranes, fabricating COF membranes at room temperature (RT) will provide a simple and captivating strategy for separation membranes. Herein, a P-COF membrane on porous alumina substrate at RT, showing 99.7% rejection of rhodamine B and excellent water permeance up to 52 L m-2 h-1 bar-1 , which can effectively purify wastewater is successfully obtained. P-COF is directly grown on alumina to form the composite membrane, which enhances the mechanical strength of COF membrane and avoids the risk of damaging the membrane structure during the transfer process of self-standing membrane. Moreover, P-COF membrane is grown at RT, which is more energy efficient than the conventional solvothermal method. Thus, it is of great significance to obtain COF membranes with excellent nanofiltration performance in a simple and mild condition to alleviate environmental and energy concerns.

Multifunctional Porous Hydrogen-Bonded Organic Frameworks: Current Status and Future Perspectives.

Hydrogen-bonded organic frameworks (HOFs), self-assembled from organic or metalated organic building blocks (also termed as tectons) by hydrogen bonding, π-π stacking, and other intermolecular interactions, have become an emerging class of multifunctional porous materials. So far, a library of HOFs with high porosity has been synthesized based on versatile tectons and supramolecular synthons. Benefiting from the flexibility and reversibility of H-bonds, HOFs feature high structural flexibility, mild synthetic reaction, excellent solution processability, facile healing, easy regeneration, and good recyclability. However, the flexible and reversible nature of H-bonds makes most HOFs suffer from poor structural designability and low framework stability. In this Outlook, we first describe the development and structural features of HOFs and summarize the design principles of HOFs and strategies to enhance their stability. Second, we highlight the state-of-the-art development of HOFs for diverse applications, including gas storage and separation, heterogeneous catalysis, biological applications, sensing, proton conduction, and other applications. Finally, current challenges and future perspectives are discussed.

A High‐Performance Nonlinear Optical Crystal with a Building Block Containing Expanded π‐Delocalization

AbstractCommon nonlinear optical (NLO) crystals consist of traditional functional building blocks with inherent optical limitation. Herein, inspired by traditional (B3O6)3− inorganic building block, we theoretically identified a new type of organic functional building blocks and then successfully synthesized the first cyamelurate NLO crystal, Ba(H2C6N7O3)2 ⋅ 8 H2O. To our surprise, the constituent (H2C6N7O3)− building block is not in structurally optimal arrangement, but Ba(H2C6N7O3)2 ⋅ 8 H2O exhibits excellent optical properties including wide band gap of 4.10 eV, very large birefringence of 0.24@550 nm, and exceptionally strong second‐harmonic generation (SHG) response of about 12×KH2PO4. Both the SHG response and birefringence are much larger than those of commercial NLO crystal β‐BaB2O4 with optimally aligned (B3O6)3− building block. Theoretical calculations suggest that the expanded π‐conjugation delocalization within (H2C6N7O3)− vs (B3O6)3− should be responsible to the enhanced performance. This work implies that there is still much room to develop new NLO crystals with excellent functional building blocks that may be longly neglected.

A High-Performance Nonlinear Optical Crystal with a Building Block Containing Expanded π-Delocalization.

Common nonlinear optical (NLO) crystals consist of traditional functional building blocks with inherent optical limitation. Herein, inspired by traditional (B3 O6 )3- inorganic building block, we theoretically identified a new type of organic functional building blocks and then successfully synthesized the first cyamelurate NLO crystal, Ba(H2 C6 N7 O3 )2 ⋅ 8 H2 O. To our surprise, the constituent (H2 C6 N7 O3 )- building block is not in structurally optimal arrangement, but Ba(H2 C6 N7 O3 )2 ⋅ 8 H2 O exhibits excellent optical properties including wide band gap of 4.10 eV, very large birefringence of 0.24@550 nm, and exceptionally strong second-harmonic generation (SHG) response of about 12×KH2 PO4 . Both the SHG response and birefringence are much larger than those of commercial NLO crystal β-BaB2 O4 with optimally aligned (B3 O6 )3- building block. Theoretical calculations suggest that the expanded π-conjugation delocalization within (H2 C6 N7 O3 )- vs (B3 O6 )3- should be responsible to the enhanced performance. This work implies that there is still much room to develop new NLO crystals with excellent functional building blocks that may be longly neglected.

Multi-Responsive Sensor Based on Porous Hydrogen-Bonded Organic Frameworks for Selective Sensing of Ions and Dopamine Molecules.

Hydrogen-bonded organic frameworks (HOFs), as an emerging porous material, have attracted increasing research interest in fluorescence sensing due to their inherent fluorescence emission units with unique physicochemical properties. Herein, based on the organic building block 3,3',5,5'-tetrakis-(4-carboxyphenyl)-1,1'-biphenyl (H4TCBP), the porous material HOF-TCBP was successfully synthesized using hydrogen bond self-assembly in a DMF solution. The fluorescence properties of the HOF-TCBP solution showed that when the concentration was high, excimers were easily formed, the PL emission was red-shifted, and the fluorescence intensity became weaker. HOF-TCBP showed good sensitivity and selectivity to metal ions Fe3+, Cr3+, and anion Cr2O72-. In addition, HOF-TCBP can serve as a label-free fluorescent sensor material for the sensitive and selective detection of dopamine (DA). HOF-based DA sensing is actually easy, low-cost, simple to operate, and highly selective for many potential interfering substances, and it has been successfully applied to the detection of DA in biological samples with satisfactory recoveries (101.1-104.9%). To our knowledge, this is the first report of HOF materials for efficient detection of the neurotransmitter dopamine in biological fluids. In short, this work widely broadens the application of HOF materials as fluorescent sensors for the sensing of ions and biological disease markers.

Controlled Release of Thymol by Cyclodextrin Metal-Organic Frameworks for Preservation of Cherry Tomatoes.

Thymol is a phenol monoterpene with potential antifungal, antioxidant and antibacterial activities. Due to the low water solubility and high volatility of thymol, encapsulation serves as an effective tool during application. In the present study, cyclodextrin (CD)-based metal-organic-frameworks (MOFs) were synthesized using α-CD, β-CD, and γ-CD as organic building blocks, and further complexed with thymol to produce three CD-MOF-THY inclusion complexes (ICs). The encapsulation content, release kinetics and fruit preservation effect of ICs were analyzed. Results showed that thymol was well embedded in γ-CD-MOFs, with the highest encapsulation content of 286.7 ± 8.4 mg/g. Release kinetics revealed that CD-MOFs exhibited a controlled release effect toward thymol for 35 days. The release kinetics of three ICs fit the Rigter-Peppas model well, with γ-CD-MOF-THY showing the lowest release rate constant of 2.85 at 50 °C, RH 75%. Moreover, γ-CD-MOF-THY exhibited a remarkable preservation performance on cherry tomatoes with the lowest decay index (18.75%) and weight loss (5.17%) after 15 days of storage, suggesting this material as a potential fresh-keeping material for fruit and vegetable preservation.

Nacre-inspired interface structure design of polymer bonded explosives toward significantly enhanced mechanical performance

Realizing effective enhancement to the structure of interface region between explosive crystals and polymer binder plays a key role in improving the mechanical properties of the current polymer bonded explosives (PBXs). Herein, inspired by the structure of natural nacre which possesses outstanding mechanical performance, a kind of nacre-like structural layer is constructed in the interface region of PBXs composites, making use of two-dimensional graphene sheets and one-dimensional bio-macromolecules of cellulose as inorganic and organic building blocks, respectively. Our results reveal that the constructed nacre-like structural layer can effectively improve the interfacial strength and then endow the PBXs composites with significantly enhanced mechanical properties involving of creep resistance, Brazilian strength and fracture toughness, demonstrating the obvious advantage of such bioinspired interface structure design strategy. In addition, the thermal conduction performance of PBXs composites also exhibits noticeable enhancement due to the remarkable phonon transport capability endowed by the as-designed nacre-like structural layer. We believe this work provides a novel design route to conquer the issue of weak interfacial strength in PBXs composites and greatly increase the comprehensive properties for better meeting the higher requirements proposed to the explosive part of weapon equipment in new era.

Reconfiguring band-edge states and charge distribution of organic semiconductor-incorporated 2D perovskites via pressure gating.

Two-dimensional (2D) semiconductor heterostructures are key building blocks for many electronic and optoelectronic devices. Reconfiguring the band-edge states and modulating their interplay with charge carriers at the interface in a continuous manner have long been sought yet are challenging. Here, using organic semiconductor-incorporated 2D halide perovskites as the model system, we realize the manipulation of band-edge states and charge distribution via mechanical-rather than chemical or thermal-regulation. Compression induces band-alignment switching and charge redistribution due to the different pressure responses of organic and inorganic building blocks, giving controllable emission properties of 2D perovskites. We propose and demonstrate a "pressure gating" strategy that enables the control of multiple emission states within a single material. We also reveal that band-alignment transition at the organic-inorganic interface is intrinsically not well resolved at room temperature owing to the thermally activated transfer and shuffling of band-edge carriers. This work provides important fundamental insights into the energetics and carrier dynamics of hybrid semiconductor heterostructures.

Toward efficient functionalization of polystyrene backbone through ketene chemistry: Synthesis, characterization, and DFT study

AbstractIn this study, polystyrene was functionalized with Meldrum's acid toward the introduction of the ketenes (CCO) system to its backbone for producing a dramatically reactive intermediate. Meldrum's acid, as a ketene source, was reacted by poly(styrene‐co‐p‐chloromethyl styrene) through a simple nucleophilic reaction to synthesize poly(styrene‐co‐styryl Meldrum's acid). Then, the pendant Meldrum's acid under thermal treatment converted to ketene intermediate resulting in highly reactive polystyrenes derivatives, which rapidly reacted by nucleophilic reagents to afford ultimate organic building blocks. The polystyrene derivatives were characterized using elemental analysis, FT‐IR, high‐resolution solid‐state NMR, thermogravimetric analysis (TGA), and differential thermogravimetric analysis (DTG). To clarify the evolutionary mechanisms of polystyrene products, density functional theory (DFT) method B3LYP with the 6–311++G(2d,p) basis set was used. We studied the preparation of polystyrene model compounds through Meldrum's acid thermolysis and nucleophilic substitution. The kinetic and thermodynamic parameters in all reactions and the structural and electronic properties of all molecules were calculated. These data exhibited that based on Gibbs Free energy values, the structure of syndiotactic polystyrene is more stable than that of isotactic polystyrene. Furthermore, it was found that the presence of an electron donor or acceptor substituent on the polystyrene structure affects the electronic bandgap.

Chirality Transfer from an Innately Chiral Nanocrystal Core to a Nematic Liquid Crystal 2: Lyotropic Chromonic Liquid Crystals.

The importance of and the difference between molecular versus structural core chirality of substances that form nanomaterials, and their ability to transmit and amplify their chirality to and within a surrounding condensed medium is yet to be exactly understood. Here we demonstrate that neat as well as disodium cromoglycate (DSCG) surface-modified cellulose nanocrystals (CNCs) with both molecular and morphological core chirality can induce homochirality in racemic nematic lyotropic chromonic liquid crystal (rac-N-LCLC) tactoids. In comparison to the parent chiral organic building blocks, D-glucose, endowed only with molecular chirality, both CNCs showed a superior chirality transfer ability. Here, particularly the structurally compatible DSCG-modified CNCs prove to be highly effective since the surface DSCG moieties can insert into the DSCG stacks that constitute the racemic tactoids. Overall, this presents a highly efficient pathway for chiral induction in an aqueous medium and thus for understanding the origins of biological homochirality in a suitable experimental system.

O2-induced emission color changing/sensing via the combination of red-emitting COF and blue-emitting halogen-bridging Cu(I) phosphor: In-situ synthesis and performance

Covalent organic frameworks (COFs) have shown virtues of structural diversity and porous diversity, due to their versatile organic building blocks. These advantages make COFs a promising host for O2 gas sensors. In this work, a porous COF (denoted as COF-X, X = Br or Cl) having halogen ions (Br or Cl ions) in its micropores was firstly synthesized as host, then Cu clusters [Cu2(PPh3)3X2] were in-situ synthesized. The obtained composite structure was discussed in detail focusing on its photophysical parameters and optical oxygen sensing performance. Probe doping ratio was determined as 2:1 (C162H120N18O12X4@C54H45X2Cu2P3, X = Br or Cl). Host COF-X showed red emission around 628 nm, while probe Cu2(PPh3)3X2 exhibited blue emission around 436 nm with lifetime of 5.21 μs and quantum yield of 0.41 under pure N2 atmosphere. Upon pure O2 atmosphere, probe Cu2(PPh3)3Br2 lifetime and quantum yield were decreased to 1.16 μs and 0.09. Probe emission intensity followed a linear calibration curve with maximum sensitivity of 20.25 (a.u.) and response/recovery time of 9/41 s. This sensitivity was by far the highest one among phosphorescent Cu(I)-based sensors. The relative emission intensity variation between dopant blue emission and host red emission led to an emission color change between blue (under pure N2 atmosphere) and red (under pure O2 atmosphere).

Analysis of lignins using 31P benchtop NMR spectroscopy: quantitative assessment of substructures and comparison to high-field NMR

Lignin is quickly emerging as a biomass-derived source for the production of some crucial organic chemistry building blocks, typically obtained from unsustainable and non-renewable petroleum feedstocks. As a complex polymer, lignin characterization is often challenging due to its random structure and multitudes of different repeating substructures. Over the last 20 years, advances in our understanding and processing of lignin, as well as important work on its characterization using 31P NMR, have led to numerous publications highlighting the many potential uses of this material. With the emergence of high-resolution benchtop NMR instruments, these types of analyses can now be accessed by many laboratories and industries that have historically not been able to take advantage of NMR due to cost or size constraints. Herein, we demonstrate that benchtop NMR is a viable technique for the 31P NMR analysis of lignin and compare our results to those obtained on a traditional high-field instrument.

Designing Ruddlesden–Popper Layered Perovskites through Their Organic Cations

Organic–inorganic layered perovskites were initially envisioned as materials for solar cells in view of their greater ambient stability compared to their 3D relatives. However, their major limitation was the insulating character of the bulky organic cations, especially in single-layer structures. This limitation was turned into an opportunity to explore organic molecules with different configurations, a journey that, to date, has delivered new materials for lighting, photocatalysis, chiro-optoelectronics, and ferroelectricity. In this Perspective, we aim to provide an outlook on the future challenges of using metal-halide Ruddlesden–Popper layered perovskites as scaffolds, including functional organic building blocks, for the creation of new hybrid materials. We envision that this research field can be empowered by establishing strong bridges with the organic chemistry and the machine-learning communities, which will help researchers to efficiently design new organic cations for exciting functionalities in this class of materials.

1,2-Amino oxygenation of alkenes with hydrogen evolution reaction

1,2-Amino oxygenation of alkenes has emerged as one of the most straightforward synthetic methods to produce β-amino alcohols, which are important organic building blocks. Thus, a practical synthetic strategy for 1,2-amino oxygenation is highly desirable. Here, we reported an electro-oxidative intermolecular 1,2-amino oxygenation of alkenes with hydrogen evolution, removing the requirement of extra-oxidant. Using commercial oxygen and nitrogen sources as starting materials, this method provides a cheap, scalable, and efficient route to a set of valuable β-amino alcohol derivatives. Moreover, the merit of this protocol has been exhibited by its broad substrate scope and good application in continuous-flow reactors. Furthermore, this method can be extended to other amino-functionalization of alkenes, thereby showing the potential to inspire advances in applications of electro-induced N-centered radicals (NCRs).

Integrated pyrazine-based porous aromatic frameworks/carbon nanotube composite as cathode materials for aqueous zinc ion batteries

Aqueous zinc-ion batteries (ZIBs) have garnered intensive focus as a new generation of environmentally friendly and low-cost energy storage devices. However, the instability of the structure caused by Zn2+ insertion/extraction and slow kinetics limit its further development. Here, we proposed a rational strategy to link electroactive organic building blocks (HATN) using dual thioether bond and then in-situ polymerize it on carbon nanotube (CNT) (PAF-205/CNT). The extensive conjugated system constructed by sulfide chain and the introduction of conductive matrix can improve its conductive properties, thus increasing the utilization rate of active sites. As expected, PAF-205/CNT as the host material for zinc-ion storage shows a high initial capacity of 328.5 mA h g−1 at 50 mA g−1, a nearly 76.2 % capacity retention after 10,000 cycles at 20 A/g and a rate capacity of 89 mA h g−1 at 20 A/g. Furthermore, experimental analyses and theoretical calculation were performed to reveal the charge storage mechanism. Also, PAF-205/CNT cathode also shows good electrochemical performance in lithium-ion batteries (LIBs). Our study provides a strategy and insight for the rational design of promising organic electroactive materials for advanced metal-ion Batteries.

ß-Sheet Induced Helical Self-Assembly Structure Formation by Dityrosine Dipeptide: Crystallographic Evidence and Other Biophysical Studies

Self-assembled structures derived from short peptides are a versatile class of organic building blocks which have shown great potential in a wide range of domains. In the current study, side-chain protected dityrosine based short peptide (TP) was synthesized, and its conformation accompanied by a self-assembly pattern was investigated through several spectroscopic studies and single crystal X-ray analysis. The single crystal X-ray analysis of TP confirmed that it exhibited a ß-sheet pattern which further self-assembled to form ß-sheet-promoted helical architectures by various noncovalent interactions. To the best of our knowledge, this is the first crystallographic report of a side-chain protected dityrosine based short peptide adopting ß-sheet-promoted helical structures. Morphological analysis of TP also revealed ß-sheet as well as helical conformations. NMR study suggested that both amide hydrogens of TP are involved in intermolecular hydrogen bonding. Moreover, CD spectroscopy established the self-assembly phenomenon of TP in the solution state by showing both corresponding ß-sheet and α-helix bands. Hirshfeld surface analysis and DFT study also concluded similar results. These kinds of small peptide units mimicking important protein secondary structures like helical assembly would be of pivotal significance as they may act as small peptidomimetics, mimicking the protein "Hotspot" area.

Use of Porphyrin Containing Porous Materials in Heterogeneous Catalyst

Due to their potential applications in catalysis, separation, gas storage, drug delivery, and biosensing, porous materials (PMs) such as porous organic polymers (POPs), polymers with intrinsic microporosity (PIMs), porous coordination polymers (PCPs), and metal–organic frameworks (MOFs), have received much attention. Various building blocks have been prepared and demonstrated various functional materials. Among the various organic building blocks, porphyrin has become one of the most important building blocks for the construction of such materials witnessed by a wide range of molecular architectures using porphyrin derivatives with various applications. Mn(III)- and Fe(III)-containing metalloporphyrins are often used to fabricate various functional molecular architectures and to mimic the extraordinary behavior of enzymes in both homogeneous and heterogeneous catalytic systems. In the case of homogeneous catalysis, Mn(III)- and Fe(III)-containing metalloporphyrins have frequent trouble with fast catalytic degradation because of µ-oxo dimer formation or ligand oxidation. To avoid the catalyst degradation, the immobilization and/or site-isolation of homogeneous catalysts using supporters such as polymers, membranes, and MOFs, are widely used strategy. In addition, they are often used to modify the surface of porous silica materials such as SBA-15, MCM-41 and MCM-48, because these porous silica materials exhibit narrow pore size distributions, high thermal stability and easy accessibility.In this presentation, we like to show the use of metalloporphyrins in various porous materials and their use as heterogeneous catalysts.References D. Y. Shin, J. H. Yoon, S. H. Kim, H. Baik, S. J. Lee,* "Immobilization of Porphyrinic Mn(III) Catalyst on a New Class of Silica Support Comprising Three-Dimensionally Interconnected Network with Two Different Sizes of Pores", Catal. Sci. Technol. 2018, 8, 6306-6310.J. Yi, H. Y. Jeong, D. Y. Shin, C. Kim, S. J. Lee,* "Mn(III)-Porphyrin Containing Heterogeneous Catalyst based on Microporous Polymeric Constituents as a New Class of Catalyst Support", ChemCatChem 2018, 10, 3974-3977.J. Yoon, H. M. Choi, S. J. Lee,* "Cu(II)Cl2 containing bispyridine-based porous organic polymer support prepared via alkyne–azide cycloaddition as a heterogeneous catalyst for oxidation of various olefins", New J. Chem. 2020, 44, 9149-9152.H. M. Choi, Y. J. Kim, E. T. Choi, S. J. Lee,* "Selective Photocatalytic Oxidative Detoxification of a Chemical Warfare Agent Simulant by Porphyrin-Containing Polymers of Intrinsic Microporocity." ACS Appl. Polym. Mater.2021, submitted .

Aminal‐Linked Porphyrinic Covalent Organic Framework for Rapid Photocatalytic Decontamination of Mustard‐Gas Simulant

AbstractCovalent organic frameworks (COFs) are appealing photocatalysts for toxic chemical degradation. Great efforts have been devoted to regulate the photocatalytic performance of COFs by tuning their organic building blocks, but the relationship between COF linkage and photochemical properties has rarely been explored. Herein, we report the synthesis and characterisation of a novel aminal‐linked porphyrinic COF, namely Por‐Aminal‐COF. Por‐Aminal‐COF (0.25 mol %) showed excellent photocatalytic activity toward the detoxification of the sulfur mustard simulant with a half‐life (t1/2) of 5 min, which is far lower than that of traditional imine‐linked Por‐COF (t1/2=16 min). Transient absorption spectroscopy indicated that the aminal linkages of Por‐Aminal‐COF facilitated the intersystem crossing process. Thus, Por‐Aminal‐COF showed higher triplet‐state generation efficiency compared with Por‐COF, consequently promoting the activation of oxygen molecular to singlet oxygen.

Aminal-Linked Porphyrinic Covalent Organic Framework for Rapid Photocatalytic Decontamination of Mustard-Gas Simulant.

Covalent organic frameworks (COFs) are appealing photocatalysts for toxic chemical degradation. Great efforts have been devoted to regulate the photocatalytic performance of COFs by tuning their organic building blocks, but the relationship between COF linkage and photochemical properties has rarely been explored. Herein, we report the synthesis and characterisation of a novel aminal-linked porphyrinic COF, namely Por-Aminal-COF. Por-Aminal-COF (0.25 mol %) showed excellent photocatalytic activity toward the detoxification of the sulfur mustard simulant with a half-life (t1/2 ) of 5 min, which is far lower than that of traditional imine-linked Por-COF (t1/2 =16 min). Transient absorption spectroscopy indicated that the aminal linkages of Por-Aminal-COF facilitated the intersystem crossing process. Thus, Por-Aminal-COF showed higher triplet-state generation efficiency compared with Por-COF, consequently promoting the activation of oxygen molecular to singlet oxygen.

A Microporous Potassium‐Organic Framework for Efficient C2H2/CO2 Separation

AbstractA novel potassium‐based metal organic framework (TCBPA‐K) was prepared by using a C3‐symmetric organic building block tris(4′‐carboxybiphenyl)amine (TCBPA). The compound has a rectangular like channel along the b axis and exhibits good selective adsorption performance. The single component gas adsorption isotherms indicated that the adsorption capacity of C2H2 is much higher than that of CO2 at 298 K and 1 bar. The isosteric adsorption enthalpies of TCBPA‐K for C2H2 and CO2 are 30.6 kJ/mol and 9.1 kJ/mol respectively. Ideal adsorbed solution theory calculation recorded the separation selectivity of C2H2/CO2 (50/50, v/v) as 3.5.