Organic Crystalline Materials Research Articles

Global Analysis of the Mechanical Properties of Organic Crystals.

Organic crystals, although widely studied, have not been considered nascent candidate materials in engineering design. Here we summarize the mechanical properties of organic crystals that have been reported over the past three decades, and we establish a global mechanical property profile that can be used to predict and identify mechanically robust organic crystals. Being composed of light elements, organic crystals populate a narrow region in the mechanical property-density space between soft, disordered organic materials and stiff, ordered materials. Two subsets of extraordinarily stiff and hard organic crystalline materials were identified and rationalized by the normalized number density, strength, and directionality of their intermolecular interactions. We conclude that future lightweight, soft, all-organic components in devices should capitalize on the greatest asset of organic single crystals-namely, the combination of long-range structural order and softness.

Global Analysis of the Mechanical Properties of Organic Crystals

AbstractOrganic crystals, although widely studied, have not been considered nascent candidate materials in engineering design. Here we summarize the mechanical properties of organic crystals that have been reported over the past three decades, and we establish a global mechanical property profile that can be used to predict and identify mechanically robust organic crystals. Being composed of light elements, organic crystals populate a narrow region in the mechanical property–density space between soft, disordered organic materials and stiff, ordered materials. Two subsets of extraordinarily stiff and hard organic crystalline materials were identified and rationalized by the normalized number density, strength, and directionality of their intermolecular interactions. We conclude that future lightweight, soft, all‐organic components in devices should capitalize on the greatest asset of organic single crystals—namely, the combination of long‐range structural order and softness.

Ion-Selective Covalent Organic Framework Membranes as a Catalytic Polysulfide Trap to Arrest the Redox Shuttle Effect in Lithium-Sulfur Batteries.

In the wake of shaping the energy future through materials innovation, lithium-sulfur batteries (LSBs) are top-of-the-line energy storage system attributed to their high theoretical energy density and specific capacity inclusive of low material costs. Despite their strengths, LSBs suffer from the cross-over of soluble polysulfide redox species to the anode, entailing fast capacity fading and inferior cycling stability. Adding to the concern, the insulating character of polysulfides lends to sluggish reaction kinetics. To address these challenges, we construct optimized polysulfide blockers-cum-conversion catalysts by accommodating the battery separator with covalent organic framework@Graphene (COF@G) composites. We settle on a crystalline TAPP-ETTB COF in the interest of its nitrogen-enriched scaffold with a regular pore geometry, providing ample lithiophilic sites for strong chemisorption and catalytic effect to polysulfides. On another front, graphene enables high electron mobility, boosting the sulfur redox kinetics. Consequently, a lithium-sulfur battery with a TAPP-ETTB COF@G-based separator demonstrates a high reversible capacity of 1489.8 mA h g-1 at 0.2 A g-1 after the first cycle and good cyclic performance (920 mA h g-1 after 400 cycles) together with excellent rate performance (827.7 mA h g-1 at 2 A g-1). The scope and opportunities to harness the designability and synthetic structural control in crystalline organic materials is a promising domain at the interface of sustainable materials, energy storage, and Li-S chemistry.

Covalent organic frameworks: Design and applications in electrochemical energy storage devices

AbstractAs an emerging class of crystalline organic material, covalent organic frameworks (COFs) possess uniform porosity, versatile functionality, and precise control over designated structures. Aside from the favorable charge and mass transport pathways offered by the porous framework, COFs can also exhibit designed reversible redox activity. In the past few years, their potential has attracted a great deal of attention for charge storage and transport applications in various electrochemical energy storage devices, and numerous design strategies have been proposed to enhance the corresponding electrochemical properties. This review summarizes the working principle and synthesis methods of COFs and discusses significant findings for supercapacitors and various rechargeable battery systems, emphasizing the representative design strategies and their underlying relationship with electrochemical performances. In addition, key advances achieved by computations are highlighted along with the challenges and prospects in this field.image

Efficient Extraction and Determination of Carbamate Pesticides in Vegetables Based on a Covalent Organic Frameworks with Acylamide Sites

It is an important challenge to effectively extract and determine pesticides in complex samples. Covalent organic frameworks (COFs) are burgeoning porous crystalline organic materials with good environmental resistance, thus demonstrating great potential as adsorbents in contaminants detection. In this work, we design and synthesize a novel COF-TpDB via 1,3,5-triformylphloroglucinol (Tp) and 4,4′-diaminobenzoylanilide (DB) as well as its packed cartridge for solid phase extraction (SPE) of carbamate pesticides. Simulation calculations showed H-bonding facilitates the adsorption interactions between the carbamate pesticides and TpDB. A method was developed by coupling TpDB as SPE sorbents with high performance liquid chromatography-ultraviolet (HPLC-UV) detection to determine trace carbamate pesticides in vegetables. The established method showed a wide linear range of 0.1–200 ng mL−1 and low limit of detections (0.005–0.05 ng mL−1) for four carbamate pesticides. The applicability of TpDB as adsorbent was investigated for determination of trace carbamate pesticides residue in vegetables with satisfactory recoveries of four carbamates in the range of 80.4–101.2%. The results demonstrated that the COF-TpDB offer great potential for efficient extraction of carbamate pesticides from complicate matrices.

Mechanical deformation and multiple thermal restoration of organic crystals: reversible multi-stage shape-changing effect with luminescence-color changes.

Shape-memory materials can be mechanically deformed and subsequently reverse the deformation upon changing the temperature. Shape-memory materials have attracted considerable attention for basic research and industrial applications, and polymer and alloy shape-memory materials have been well studied; however, it is formidably challenging to develop functional shape-memory materials, such as materials with multi-stage and anisotropic shape changes and shape changes accompanied by changes in color and light emission. Here, we found a reversible multi-stage shape-changing effect after mechanical deformation in a molecular crystal induced by multi-step thermal phase transitions with reversible shape changes and luminescence-color changes. Using single-crystal structure and thermal analyses as well as mechanical property measurements, we found that the reversible multi-stage shape-changing effect was achieved by a combination of a twinning deformation and multi-step thermal phase transitions. The changes in the crystal shape and luminescence suggest novel strategies for imparting known shape-memory materials with additional functionalities.

Enhanced proton conduction of crystalline organic salt hybrid membranes and the performance of fuel cells

The hybrid Nafion membranes of a hydrogen-bonded crystalline organic salt material are used for proton conduction and proton exchange membrane fuel cell applications.

Nitrogen-rich covalent organic frameworks: a promising class of sensory materials

Covalent organic frameworks (COFs) have emerged as highly crystalline porous organic materials. Their potential has been demonstrated for use in various applications, particularly sensing with the nitrogen-rich analogs.

Three-Dimensional Covalent Organic Frameworks with hea Topology

Three-dimensional (3D) covalent organic frameworks (COFs) are a new type of crystalline organic porous material, which have great application potential in various fields due to their complex pore s...

Accurate Analysis of Anisotropic Carrier Mobility and Structure-property Relationships in Organic BOXD Crystalline Materials.

Charge mobility is an essential factor of organic crystalline materials. Although many investigators have made important progress, the exact relationship between the crystal structure and carrier mobility remains to be clarified. Fortunately, a series of bis-1,3,4-oxadiazole derivatives have been successfully prepared and reported. They have similar main molecular fragments but different crystal packing modes, which provide an ideal research objective for studying the effect of molecular packing on charge mobility in organic photoelectric conversion systems. In this work, the charge mobilities of these molecules are systematically evaluated from the perspective of first-principles calculation, and the effect of a molecular overlap on orbital overlap integral and final charge carrier mobility is fully discussed. It can be seen that the small intermolecular distance (less than 6 Å) is the decisive factor to achieve high electron mobility in π stacking, and better mobility can be obtained by increasing the hole migration distance appropriately. A larger dihedral angle of anisotropy is an important point limiting the charge mobility in the herringbone arrangement. It is hoped that the correlation results between the crystal structure and mobility can assist the experimental study and provide an effective way to improve the photoelectric conversion efficiency of the organic semiconductor devices and multiple basis for multiscale material system characterization and material information.

Multifunctional Deformable Organic Semiconductor Single Crystals.

We report the first organic semiconductor crystal with a unique combination of properties that can be used as a multifunctional optoelectronic device. Mechanically flexible single crystals of 9,10-bis(phenylethynyl)anthracene (BPEA) can function as a phototransistor, photoswitch, and an optical waveguide. The material can exist as two structurally different solid phases, with single crystals of one of the phases being elastic at room temperature while those of the other are brittle and become plastic at higher temperature. The output and transfer characteristics of the devices were characterized by measuring the generation and temporal response of the switching of the photogenerated current. The current-voltage characteristics of both phases exhibit linearity and symmetry about the positive and negative voltages. The crystals transmit light in the telecommunications range with significantly low optical loss for an organic crystalline material.

Multifunctional Deformable Organic Semiconductor Single Crystals

AbstractWe report the first organic semiconductor crystal with a unique combination of properties that can be used as a multifunctional optoelectronic device. Mechanically flexible single crystals of 9,10‐bis(phenylethynyl)anthracene (BPEA) can function as a phototransistor, photoswitch, and an optical waveguide. The material can exist as two structurally different solid phases, with single crystals of one of the phases being elastic at room temperature while those of the other are brittle and become plastic at higher temperature. The output and transfer characteristics of the devices were characterized by measuring the generation and temporal response of the switching of the photogenerated current. The current–voltage characteristics of both phases exhibit linearity and symmetry about the positive and negative voltages. The crystals transmit light in the telecommunications range with significantly low optical loss for an organic crystalline material.

Biogeochemical properties and potential risk of shallow arsenic-rich sediment layers to groundwater quality in Western Bangladesh.

The arsenic-contaminated groundwater has attracted attention in much south and southeast Asian deltas, however, mainly on the deep aquifers. Here, arsenic (As) concentration and its fractionation of the sediment cores in a shallow aquifer in Bangladesh were investigated using ICP-MS, FE-EPMA, XRD and 14C-AMS chronology techniques. The results of the present study indicated that the peak concentrations of As (54.7-79.1µg/g) were in peat layers (at a depth of 7.5-8.0m). Several types of iron (oxyhidr)oxides and framboidal pyrite, which contain As also, were found in the peat samples. The high concentrations of As were in an exchangeable form, As-bearing iron crystalline and As-bearing organic materials. We revealed that the As-rich peat layers were formed from 3170 to 3901cal yrs before, due to the sea level decrease in this area. The 16S rRNA gene-based phylogenetic analysis revealed that the bacterial strains in the As-rich peats were mainly affiliated with genera Acinetobacter, Enterobacter, Escherichia, Bacillus, Clostridiaceae and Acinetobacter. The geo-accumulation index (Igeo) and ecological risk index assessment were calculated for the sediments, which shows that As-rich sediment layers were in range of moderately to heavily contaminated and considerable classes, respectively. Under the permanent saturated condition, the As-rich peat layers should be considered as an important potential driver of the groundwater As in this area.

Covalent Organic Framework Membranes for Efficient Chemicals Separation

Covalent organic frameworks (COFs) are an emerging class of organic porous crystalline materials that are composed entirely by organic linkers and connected by strong covalent bonds. The unique characteristics including well‐ordered and tailorable pore channels, high and permanent porosity, excellent thermostability and chemical stability, and ease of functionalization enable COFs to perfectly meet the requirements for the fabrication of advanced separation membranes. Significant progress has been made in the preparation and application of COF membranes over the past few years. Herein, the structure—performance relationship of COF materials on membrane separation is first proposed. The effects of the intrinsic properties of COF materials on membrane separation performance are systematically summarized. The fabrication methods of COF membranes, including both bottom‐up strategy (in situ growth and interface‐assisted synthesis) and top‐down strategy (blending and layer‐by‐layer [LBL] stacking), are then discussed in detail. The application of COF membranes in gas separation (H2 purification, CO2 capture, hydrocarbon separation) and liquid phase separation (water treatment, organic solvent nanofiltration, pervaporation) is highlighted. Finally, the remaining challenges and issues to be resolved in the COF membranes are prospected from the perspective of COF materials.

Ice nucleation ability of ammonium sulfate aerosol particles internally mixed with secondary organics

Abstract. The abundance of aerosol particles and their ability to catalyze ice nucleation are key parameters to correctly understand and describe the aerosol indirect effect on the climate. Cirrus clouds strongly influence the Earth's radiative budget, but their effect is highly sensitive to their formation mechanism, which is still poorly understood. Sulfate and organics are among the most abundant aerosol components in the troposphere and have also been found in cirrus ice crystal residuals. Most of the studies on ice nucleation at cirrus cloud conditions looked at either purely inorganic or purely organic particles. However, particles in the atmosphere are mostly found as internal mixtures, the ice nucleation ability of which is not yet fully characterized. In this study, we investigated the ice nucleation ability of internally mixed particles composed of crystalline ammonium sulfate (AS) and secondary organic material (SOM) at temperatures between −50 and −65 ∘C. The SOM was generated from the ozonolysis of α-pinene. The experiments were conducted in a large cloud chamber, which also allowed us to simulate various aging processes that the particles may experience during their transport in the atmosphere, like cloud cycling and redistribution of the organic matter. We found that the ice nucleation ability of the mixed AS / SOM particles is strongly dependent on the particle morphology. Small organic mass fractions of 5 wt %–8 wt % condensed on the surface of AS crystals are sufficient to completely suppress the ice nucleation ability of the inorganic component, suggesting that the organic coating is evenly distributed on the surface of the seed particles. In this case, the ice nucleation onset increased from a saturation ratio with respect to ice Sice∼1.30 for the pure AS crystals to ≥1.45 for the SOM-coated AS crystals. However, if such SOM-coated AS crystals are subjected to the mentioned aging processes, they show an improved ice nucleation ability with the ice nucleation onset at Sice∼1.35. We suggest that the aging processes change the particle morphology. The organic matter might redistribute on the surface to form a partially engulfed structure, where the ice-nucleation-active sites of the AS crystals are no longer completely masked by the organic coating, or the morphology of the organic coating layer might transform from a compact to a porous structure. Our results underline the complexity in representing the ice nucleation ability of internally mixed particles in cloud models. They also demonstrate the need to further investigate the impact of atmospheric aging and cloud processing on the morphology and related ice nucleation ability of internally mixed particles.

From the Mechanism to the Device in Polymer-Assisted Rubrene Crystallization

The rational design of organic crystalline materials is exceedingly challenging owing to the insufficient understanding of crystallization mechanisms. Here, we used a polymer (polystyrene) as a crystallization medium for an organic semiconductor (rubrene). This enabled a slow crystallization process whose mechanism was elucidated via direct transmission electron microscopy imaging and further employed to control crystallization and fabricate devices based on rubrene crystals. The elucidated mechanism involved (1) the initial formation of amorphous aggregates; (2) nucleation within the aggregates; (3) crystal growth; (4) break up into single nanocrystals; and (5) oriented attachment of nanocrystals to form platelet-like crystals. This mechanistic insight indicated that uniform nonclassical nucleation can be realized using a precise temperature control, leading to high-quality rubrene crystals. By employing this methodology, we fabricated solution-processed organic field-effect transistors (OFETs) and organic phototransistors (OPTs) that exhibited high mobility, reproducibility, and environmental stability. The devices showed an average mobility of 1 ± 0.8 cm2 V–1 s–1, a threshold voltage of −10 ± 6 V, and an on/off ratio of up to 106. Under white light irradiation, rubrene OPTs exhibited strong photoresponse with a photo/dark current ratio of P ≈ 105. Our work demonstrated that mechanistic information can be employed to fabricate high-quality OFETs, having implications for the rational design of crystalline organic electronic materials.

Proton Conduction Mechanism for Anhydrous Imidazolium Hydrogen Succinate Based on Local Structures and Molecular Dynamics.

Anhydrous organic crystalline materials incorporating imidazolium hydrogen succinate (Im-Suc), which exhibit high proton conduction even at temperatures above 100 °C, are attractive for elucidating proton conduction mechanisms toward the development of solid electrolytes for fuel cells. Herein, quantum chemical calculations were used to investigate the proton conduction mechanism in terms of hydrogen-bonding (H-bonding) changes and restricted molecular rotation in Im-Suc. The local H-bond structures for proton conduction were characterized by vibrational frequency analysis and compared with corresponding experimental data. The calculated potential energy surface involving proton transfer (PT) and imidazole (Im) rotational motion showed that PT between Im and succinic acid was a rate-limiting step for proton transport in Im-Suc and that proton conduction proceeded via the successive coupling of PT and Im rotational motion based on a Grotthuss-type mechanism. These findings provide molecular-level insights into proton conduction mechanisms for Im-based (or -incorporated) H-bonding organic proton conductors.

A Two-Dimensional Polyimide-Graphene Heterostructure with Ultra-fast Interlayer Charge Transfer.

Two‐dimensional polymers (2DPs) are a class of atomically/molecularly thin crystalline organic 2D materials. They are intriguing candidates for the development of unprecedented organic–inorganic 2D van der Waals heterostructures (vdWHs) with exotic physicochemical properties. In this work, we demonstrate the on‐water surface synthesis of large‐area (cm2), monolayer 2D polyimide (2DPI) with 3.1‐nm lattice. Such 2DPI comprises metal‐free porphyrin and perylene units linked by imide bonds. We further achieve a scalable synthesis of 2DPI‐graphene (2DPI‐G) vdWHs via a face‐to‐face co‐assembly of graphene and 2DPI on the water surface. Remarkably, femtosecond transient absorption spectroscopy reveals an ultra‐fast interlayer charge transfer (ca. 60 fs) in the resultant 2DPI‐G vdWH upon protonation by acid, which is equivalent to that of the fastest reports among inorganic 2D vdWHs. Such large interlayer electronic coupling is ascribed to the interlayer cation–π interaction between 2DP and graphene.

A Two‐Dimensional Polyimide‐Graphene Heterostructure with Ultra‐fast Interlayer Charge Transfer

AbstractTwo‐dimensional polymers (2DPs) are a class of atomically/molecularly thin crystalline organic 2D materials. They are intriguing candidates for the development of unprecedented organic–inorganic 2D van der Waals heterostructures (vdWHs) with exotic physicochemical properties. In this work, we demonstrate the on‐water surface synthesis of large‐area (cm2), monolayer 2D polyimide (2DPI) with 3.1‐nm lattice. Such 2DPI comprises metal‐free porphyrin and perylene units linked by imide bonds. We further achieve a scalable synthesis of 2DPI‐graphene (2DPI‐G) vdWHs via a face‐to‐face co‐assembly of graphene and 2DPI on the water surface. Remarkably, femtosecond transient absorption spectroscopy reveals an ultra‐fast interlayer charge transfer (ca. 60 fs) in the resultant 2DPI‐G vdWH upon protonation by acid, which is equivalent to that of the fastest reports among inorganic 2D vdWHs. Such large interlayer electronic coupling is ascribed to the interlayer cation–π interaction between 2DP and graphene.

Self-assembling crystalline peptide microrod for neuromorphic function implementation

Self-assembling crystalline peptide microrod for neuromorphic function implementation