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This work conducts a comprehensive theoretical study on the non‐covalent complexation between cyclocarbons and C60 fullerene for the first time. The binding energy between cyclocarbons and C60 fullerene is significantly stronger than that between two C18 or two C60 fullerenes, indicating a particularly strong affinity. The cyclocarbons and C60 fullerene can spontaneously assemble into complexes in the gas phase at room temperature, and the hydrophobic effect caused by the solvent environment can promote this binding. The binding strength with C60 fullerene increases almost linearly with the increase of cyclocarbon size, and the C34@C60 dimer exhibits a perfect nano‐Saturn structure. As the ring size increases, the angle between the two cyclocarbons of the 2 : 1 trimers formed by cyclocarbons and C60 fullerene gradually decreases. In C60@2 C34 trimer, the fullerene is symmetrically surrounded by two cyclocarbons. The results on the trimers formed by cyclocarbon and C60 fullerenes in a 1 : 2 ratio showed when the cyclocarbon sandwiched between two fullerenes is not quite large, the trimers exhibit an ideal dumbbell‐like structure, and the presence of the first fullerene has a significant synergistic effect on the binding of the second one. The cyclocarbon greatly promotes the dimerization of fullerenes, which acted as a "molecular glue". [ABSTRACT FROM AUTHOR]

Two different types of chiral stationary phases, based on Pirkle's design, were created by attaching chiral selectors to 3‐mercapto silica gel. To prepare the enantiomeric selectors, 3,5‐dinitrobenzoyl and naphthyl groups were sequentially added to a chiral 1,2‐diaminocyclohexane core. The chiral selectors demonstrated enantioselectivity towards ibuprofen enantiomers in solution, as confirmed by 1H NMR spectroscopy, and in initial HPLC testing, the enantiomeric selectors showed enantioselectivity for selected racemic solutes (viz., α = 1.27 for1,1′‐bi‐(2‐naphthol)). Molecular docking studies revealed that the chiral selectors had a bent structure and a cleft‐like cavity where the analyte could be held during complexation while establishing H‐bonding and π–π stacking interactions. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Compounds with magnetic bistability is highly attractive for the construction of switches, thermal sensors, information‐storage media and memory devices. Herein, we report a crystalline fullerene radical anion salt [Na(THF)5]C60 (1), obtained by the reduction of C60 with Na in solution, which exhibits magnetic bistability accompanied with one magnetostructural transition, giving low temperature (LT), high temperature (HT) phases and a metastable phase. Fullerene radical anions (C60•‐) in the structure were found arranged into a three‐dimensional close‐packed honeycomb subnetwork with hollow channels occupied by complex cations [Na(THF)5]+ as spacers. The magnetic bistability is attributed to structural transitions as the LT−IT phase transition was associated with the orientational disorder of fullerene anions and the distortion of the complex cations [Na(THF)5]+ in the 3D packing of fullerene anions. [ABSTRACT FROM AUTHOR]

The interfacial interaction between HMX molecules and coating materials is the key to the safety performance of explosives and has received extensive attention. However, screening suitable coating agents to enhance the interfacial effect to obtain high-energy and low-sensitivity explosives has long been a major challenge. In this work, HMX-PEI/rGO/g-C3N4 (HPrGC) composites were innovatively prepared by a multi-level coating strategy of two-dimensional graphite rGO and g-C3N4. The g-C3N4 used for desensitization has a rich π-conjugated system and shows outstanding ability in reducing friction sensitivity. The hierarchical structure of HPrGC formed by electrostatic self-assembly and π-π stacking can effectively dissipate energy accumulation under heat and mechanical stimulation through structural evolution, thus exhibiting a prominent synergistic desensitization effect on HMX. The results show that rGO/g-C3N4 coating has no effect on the crystal structure and chemical structure of HMX. More importantly, the perfect combination of g-C3N4 and rGO endows HPrGC with enhanced thermal stability and ideal mechanical sensitivity (IS: 21 J, FS: 216 N). Obviously, the new fabrication of HPrGC enriches the variety of desensitizer materials and helps to deepen the understanding of the interaction between explosives and coatings. [ABSTRACT FROM AUTHOR]

Ethyl 2-[(2-oxo-2H-chromen-6-yl)oxy]acetate, C13H12O5, a member of the pharmacologically important class of coumarins, crystallizes in the monoclinic C2/c space group in the form of sheets, within which molecules are related by inversion centers and 21 axes. Multiple C—H...O weak hydrogen-bonding interactions reinforce this pattern. The planes of these sheets are oriented in the approximate direction of the ac face diagonal. Intersheet interactions are a combination of coumarin system π–π stacking and additional C—H...O weak hydrogen bonds between ethyl acetoxy groups.

Colorectal cancer (CRC) is the second leading cause of cancer mortality worldwide. At initial diagnosis, approximately 20% of patients are diagnosed with metastatic CRC (mCRC). Although the APC‒Asef interaction is a well-established target for mCRC therapy, the discovery and development of effective and safe drugs for mCRC patients remains an urgent and challenging endeavor. In this study, we identified a novel structural scaffold based on MAI inhibitors, the first-in-class APC‒Asef inhibitors we reported previously. ONIOM model-driven optimizations of the N-terminal cap and experimental evaluations of inhibitory activity were performed, and 24-fold greater potency was obtained with the best inhibitor compared to the parental compound. In addition, the cocrystal structure validated that the two-layer π‒π stacking interactions were essential for inhibitor stabilization in the bound state. Furthermore, in vitro and in vivo studies have demonstrated that novel inhibitors suppressed lung metastasis in CRC by disrupting the APC‒Asef interaction. These results provide an intrinsic structural basis to further explore drug-like molecules for APC‒Asef-mediated CRC therapy.

Cation‐π interactions, often found in protein assemblies, are characterized by favorable electrostatic interactions between an aromatic π‐electron surface and a positively charged species. There are evidences that reveal the importance of cation‐π interactions between arginine and aromatic residues in protein structure and function. In this paper, the effect of cation‐π interactions on the aggregation propensity of peptides derived from human islet polypeptide (hIAPP) was explored using UV resonance Raman and fluorescence spectroscopy. By employing an analog of hIAPP22–29 in which Phe‐23 is replaced with tryptophan (NWGAILSS), we were able to demonstrate an increase in the amyloidogenic propensity of this mutant in the presence of Zn2+ that is attributable to cation‐π interactions. In contrast, no cation‐π interactions were observed when the cationic F23R analog of hIAPP22–29 (NRGAILSS) was allowed to interact with NWGAILSS. From these observations, it was surmised that in these peptides, the dominant interaction between arginine and tryptophan involves the π‐cloud of the guanidino group and the indole ring, not cation‐π interactions. The spectroscopic data, supported by density functional theory‐based simulation results, suggest that arginine‐tryptophan interaction involves π‐π stacking where the guanidino group is oriented parallel to the indole ring. These hydrophobic interactions, coupled with the hydrotropic effect of the guanidine functionality of arginine, led to a delay in the aggregation kinetics of NWGAILSS. These unique interactions were further exploited to design a peptide inhibitor of full‐length amylin self‐assembly. [ABSTRACT FROM AUTHOR]

Neutral aqueous organic redox flow batteries (AORFBs) hold the potential to facilitate the transition of renewable energy sources from auxiliary to primary energy, the commercial production of anolyte materials still suffers from insufficient performance of high‐concentration and the high cost of the preparation problem. To overcome these challenges, this study provides a hydrothermal synthesis methodology and introduces the charged functional groups into hydrophobic naphthalene diimide cores, and prepares a series of high‐performance naphthalene diimide anolytes. Under the synergistic effect of π–π stacking and H‐bonding networks, the naphthalene diimide exhibits excellent structural stability and the highest water solubility (1.85 M for dex‐NDI) reported to date. By employing the hydrothermal method, low‐cost naphthalene diimides are successfully synthesized on a hundred‐gram scale of $0.16 g−1 ($2.43 Ah−1), which is also the lowest price reported to date. The constructed full battery achieves a high electron concentration of 2.4 M, a high capacity of 54.4 Ah L−1, and a power density of 318 mW cm−2 with no significant capacity decay observed during long‐duration cycling. These findings provide crucial support for the commercialization of AORFBs and pave the way for revolutionary developments in neutral AORFBs. [ABSTRACT FROM AUTHOR]

An extremely effective photocatalytic complex, PtLCl2 (1), was synthesized with (4-([2,2':6',2''-terpyridin]-4'-yl)phenyl)boronic acid as ligand and further characterized through single crystal X-ray diffraction, X-ray photoelectron spectroscopy and UV-vis spectrum. Multipoint hydrogen bonds and three kinds of π-π stacking interactions are observed in the supramolecular structure of 1. More significantly, the Pt(II) complex exhibits outstanding photocatalytic degradation efficiency (94.76%) for methyl orange within 120 min under visible light irradiation. The kinetic rate constant (k) for 1 (10 mg) is 0.02505 min−1, which is approximately 70 times higher than that of the ligand (0.00036 min−1). Moreover, its photocatalysis mechanism proposed that ·O2− and h+ were the main active species for MO degradation, providing a great prospect for development of a new efficient photocatalytic complex. [ABSTRACT FROM AUTHOR]

π–π stacking are omnipresent interactions, crucial in many areas of chemistry, and often studied using quantum chemical methods. Here, we report a simple and computationally efficient method of estimating the binding energies of stacked polycyclic aromatic hydrocarbons based on steered molecular dynamics. This method leverages the force field parameters for accurate calculation. The presented results show good agreement with those obtained through DFT at the ωB97X-D3/cc-pVQZ level of theory. It is demonstrated that this force field-driven SMD method can be applied to other aromatic molecules, allowing insight into the complexity of the stacking interactions and, more importantly, reporting π–π stacking energy values with reasonable precision. [ABSTRACT FROM AUTHOR]

Ethyl 2-[(2-oxo-2H-chromen-6-yl)­oxy]acetate, C13H12O5, a member of the pharmacologically important class of coumarins, crystallizes in the monoclinic C2/c space group in the form of sheets, within which mol­ecules are related by inversion centers and 21 axes. Multiple C—H⋯O weak hydrogen-bonding inter­actions reinforce this pattern. The planes of these sheets are oriented in the approximate direction of the ac face diagonal. Inter­sheet inter­actions are a combination of coumarin system π–π stacking and additional C—H⋯O weak hydrogen bonds between ethyl acet­oxy groups. [ABSTRACT FROM AUTHOR]

Colorectal cancer (CRC) is the second leading cause of cancer mortality worldwide. At initial diagnosis, approximately 20% of patients are diagnosed with metastatic CRC (mCRC). Although the APC‒Asef interaction is a well-established target for mCRC therapy, the discovery and development of effective and safe drugs for mCRC patients remains an urgent and challenging endeavor. In this study, we identified a novel structural scaffold based on MAI inhibitors, the first-in-class APC‒Asef inhibitors we reported previously. ONIOM model-driven optimizations of the N-terminal cap and experimental evaluations of inhibitory activity were performed, and 24-fold greater potency was obtained with the best inhibitor compared to the parental compound. In addition, the cocrystal structure validated that the two-layer π‒π stacking interactions were essential for inhibitor stabilization in the bound state. Furthermore, in vitro and in vivo studies have demonstrated that novel inhibitors suppressed lung metastasis in CRC by disrupting the APC‒Asef interaction. These results provide an intrinsic structural basis to further explore drug-like molecules for APC‒Asef-mediated CRC therapy. This study elucidated an ONIOM model-driven design and optimization of inhibitors targeting APC‒Asef based on the unique "Sandwich" π‒π interactions. [Display omitted] [ABSTRACT FROM AUTHOR]

The aggregation‐induced emission (AIE) properties of a systematic series of naphthalene diimides (NDIs) varying the chain length at the imide positions have been studied. A solvophobic collapse of NDI units through the flash injection of THF NDI solutions in sonicating water triggers the formation of stable suspensions with enhanced fluorescence emissions. Shorter chains favor the π‐π stacking of NDI units through H‐aggregation producing a strong AIE effect showing remarkably high quantum yields that have not been observed for non core‐substitued NDIs previously. On the other hand, NDIs functionalized with longer chains lead to more disordered domains where π‐π stacking between NDI units is mainly given by J‐aggregation unfavoring the AIE effect. [ABSTRACT FROM AUTHOR]

The π-π stacking is a well-recognized intermolecular interaction that is responsible for the construction of electron hopping channels in numerous conducting frameworks/aggregates. However, the exact role of π-to-π channels within typical single crystalline organic semiconductors remains unclear as the orientations of these molecules are diverse, and their control usually requires additional side chain groups that misrepresent the intrinsic properties of the original semiconducting molecules. Therefore, the construction of conduction channels with intrinsic π-π stacking in the molecule-based device is crucial for the utilization of their unique transport characteristics and understanding of the transport mechanism. To this end, we present a molecular intercalation strategy that integrates two-dimensional layered materials with functional organic semiconductor molecules for functional molecule-based electronics. Various organic semiconductor molecules can be effectively intercalated into the van der Waals gaps of semi-metallic TaS2 with π-π stacking configuration and controlled intercalant content. Our results show that the vertical charge transport in the stacking direction shows a tunneling-dominated mechanism that strongly depends on the molecular structures. Furthermore, we demonstrated a new type of molecule-based vertical transistor in which TaS2 and π-π stacked organic molecules function as the electrical contact and the active channel, respectively. On/off ratios as high as 447 are achieved under electrostatic modulation in ionic liquid, comparable to the current state-of-the-art molecular transistors. Our study provides an ideal platform for probing intrinsic charge transport across π-π stacked conjugated molecules and also a feasible approach for the construction of high-performance molecule-based electronic devices. [ABSTRACT FROM AUTHOR]

In the hydrated title salt, (C10H8NO2)2[SnCl6]·2H2O, the tin(IV) atom is located about a center of inversion. In the crystal structure, the organic cation, the octahedral inorganic anion and the water molecule of crystallization interact through O—H...O, N—H...O and O—H...Cl hydrogen bonds, supplemented by weak π–π stacking between neighboring cations, and C—Cl...π interactions.

The arene‐arene interactions between electron‐rich and deficient aromatics have been less understood. Herein, we focus on a [60]fullerene π‐surface as an electron‐deficient aromatics. Using a 1H signal of H2O@C60 as a magnetic probe, the presence of benzene–fullerene interactions was confirmed. To investigate substituent effects on the noncovalent arene‐fullerene interactions, NMR titration experiments were carried out using an open‐[60]fullerene and a series of substituted benzenes, i. e. PhX (X=NO2, CN, Cl, OMe, H, CH3, and NH2), demonstrating a 1 : 2 stoichiometry with a positive correlation between stabilization energies upon the first association (ΔG1) and Hammet constants (σm). The destabilization of the self‐assembled structure for X=OMe with a σ‐withdrawing nature clearly showed direct through‐space substituent‐π interactions describable by the Wheeler‐Houk model while the second association was suggested to be considerably perturbed by the secondary effects. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Fine‐tuning of the electron‐deficient unit in A‐DA1D‐A typed small‐molecule acceptors (SMAs) plays a crucial role in developing efficient SMAs for organic solar cells (OSCs). Here, we developed a SMA based on benzo[4,5]thieno[2,3‐b]quinoxaline, designated as QW1, as well as three SMAs based on 1‐methylindoline‐2,3‐dione, identified as QW2, QW3, and QW4. Compared with QW2, QW1 displays slightly blue‐shifted absorption spectra and a lower LUMO energy level due to the stronger electron‐withdrawing capability of BTQx in contrast to MDO. On the other hand, the introduction of a bromine atom in QW3 and QW4 causes a blue shift in absorption and a reduction in the LUMO energy level compared to QW2. Density functional theory analysis reveals that QW1 exhibits the best molecular planarity, which endows QW1 with larger electron mobility and tighter molecular stacking. Consequently, PM6:QW1 device affords a better efficiency of 15.63% than those of the devices based on QW2 (14.25%), QW3 (13.21%) and QW4 (15.03%). Moreover, the QW4‐based device yields the highest open‐circuit voltage of 0.933 V, and the PM6:L8‐BO:QW4 ternary device realizes a PCE of 19.03%. Overall, our work demonstrates that regulation of electron‐deficient central units is an effective strategy to improve the photovoltaic performance of the resulting A‐DA1D‐A SMAs. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Fine‐tuning of the electron‐deficient unit in A‐DA1D‐A typed small‐molecule acceptors (SMAs) plays a crucial role in developing efficient SMAs for organic solar cells (OSCs). Here, we developed a SMA based on benzo[4,5]thieno[2,3‐b]quinoxaline, designated as QW1, as well as three SMAs based on 1‐methylindoline‐2,3‐dione, identified as QW2, QW3, and QW4. Compared with QW2, QW1 displays slightly blue‐shifted absorption spectra and a lower LUMO energy level due to the stronger electron‐withdrawing capability of BTQx in contrast to MDO. On the other hand, the introduction of a bromine atom in QW3 and QW4 causes a blue shift in absorption and a reduction in the LUMO energy level compared to QW2. Density functional theory analysis reveals that QW1 exhibits the best molecular planarity, which endows QW1 with larger electron mobility and tighter molecular stacking. Consequently, PM6:QW1 device affords a better efficiency of 15.63% than those of the devices based on QW2 (14.25%), QW3 (13.21%) and QW4 (15.03%). Moreover, the QW4‐based device yields the highest open‐circuit voltage of 0.933 V, and the PM6:L8‐BO:QW4 ternary device realizes a PCE of 19.03%. Overall, our work demonstrates that regulation of electron‐deficient central units is an effective strategy to improve the photovoltaic performance of the resulting A‐DA1D‐A SMAs. [ABSTRACT FROM AUTHOR]

The crystal structure of tetrachloroferrate(III) complex with methylene blue, [Mb]+[FeCl4]− (where [Mb]+ methylthioninium or 3,7-bis(dimethylamino)-phenothiazine-5-ium cation), has been prepared by mechanochemical way and studied by the single crystal X-ray crystallography. The crystal structure of title compound is built from by [FeCl4]− tetrahedral ion and planar [Mb]+ counter ions. The [Mb]+ cation is linked in the 3D network by the C–H···Cl hydrogen bonds and is stacked in an antiparallel fashion with the sulfur atom disposed alternatively on an opposite sides of the stacking. The interplanar distance between two neighboring aromatic cycles is 3.431 Å, and a centroids–centroids distance between thiazine rings is 3.975 Å. Dihedral angle between aromatic rings is 1.6°. Intermolecular short contacts were analyzed by 3D Hirshfeld surfaces method and 2D fingerprint plots. Intermolecular interaction energy between two neighboring Mb+ cation pair was calculated by using of CE-B3LYP/6-31G(d,p) theoretical level. The π···π stacking interactions were found plays an important role in the crystal structure formation of the FeCl3 complex with methylene blue, and calculation by the CrystalExlorer17.5 program indicates that π···π interaction energy between two neighboring methylene blue cations is −33.5 kJ/mol. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Owing to the function of manipulating light absorption distribution, tandem organic solar cells containing multiple sub‐cells exhibit high power conversion efficiencies. However, there is a substantial challenge in precisely controlling the inter‐subcells carrier migration which determines the balance of charge transport across the entire device. The conductivity of "nanowires"‐like conducting channel in interconnecting layer between sub‐cells should be improved which calls for fine engineering on the morphology of polyelectrolyte in interconnecting layer. Here, we develop a simple method to effectively manipulating the domains of conductive components in commercially available polyelectrolyte PEDOT:PSS. The use of poor solvent could effectively modify the configuration of polystyrene sulfonic acid and thus the space for conductive components. Based on our strategy, the insulated shells wrapping conductive domains are thinned and the efficiencies of tandem organic solar cells are improved. We believe our method might provide guidance for the manufacture of tandem organic solar cells. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Owing to the function of manipulating light absorption distribution, tandem organic solar cells containing multiple sub‐cells exhibit high power conversion efficiencies. However, there is a substantial challenge in precisely controlling the inter‐subcells carrier migration which determines the balance of charge transport across the entire device. The conductivity of "nanowires"‐like conducting channel in interconnecting layer between sub‐cells should be improved which calls for fine engineering on the morphology of polyelectrolyte in interconnecting layer. Here, we develop a simple method to effectively manipulating the domains of conductive components in commercially available polyelectrolyte PEDOT:PSS. The use of poor solvent could effectively modify the configuration of polystyrene sulfonic acid and thus the space for conductive components. Based on our strategy, the insulated shells wrapping conductive domains are thinned and the efficiencies of tandem organic solar cells are improved. We believe our method might provide guidance for the manufacture of tandem organic solar cells. [ABSTRACT FROM AUTHOR]

π‐π interactions, serving as a pivotal driving force, hold enduring significance in the realm of drug delivery system development, primarily due to the prevalence of aromatic moieties in a substantial number of clinically relevant pharmaceutical compounds. Herein, we constructed a novel carbon nitride compound called PTCNx, featuring a large π‐conjugated skeleton, and employed it as a carrier for delivering aromatic clinical drugs for the first time. We conducted sequence characterization of their chemical structure, optical properties, and morphology, along with extensive research to analyze their significant enhancement in drug loading capacity. Of particular note was the exceptional loading efficiency of Doxorubicin (DOX) under alkaline conditions, achieving an unexpected 99 % efficacy, significantly surpassing the capabilities of traditional carbon nitrides with limited π‐conjugated systems. Cell tests illustrated that PTCN550 carrier exhibited favorable biocompatibility and low toxicity for normal and tumor cells, showing its potential as a drug carrier. However, PTCN550‐DOX complex effectively inhibited both A549 and CNE‐2Z tumor cells. And it demonstrated more effective anti‐tumor activity for CNE‐2Z than for A549 cells. This study marks a significant milestone, representing the inaugural endeavor to elucidate the improvement in loading capacity through the strategic extension of the π‐conjugated system design paradigm. [ABSTRACT FROM AUTHOR]

In this manuscript, the potential utility of 6CF macrocyclic oligofuran is theoretically investigated to create novel nanotubes. The energetic, electronic, structural and topological properties of π-stacked systems are examined at B3LYP/6-31 + G(d), wB97XD/6-31 + G(d) and M06-2X/6-31 + G(d) levels of theory. The findings indicate that the self-assembly of 6CF macrocyclic oligofurans can be considered to create organic nanotubes through π–π stacking. The strength and nature of π-π interactions are examined using the atoms in molecules (AIM) approach. Meaningful relationships are obtained between stability, electronic properties and the number of stacked π-conjugated macrocyclic oligofurans. The stability and polarisability of π-stacked systems are amplified by increasing number of macrocycles. Reverse behaviours are found for the values of band gap, electronic chemical potential and first ionisation energy. [ABSTRACT FROM AUTHOR]

Two new copper dimers, namely, bis(dimethyl sulfoxide)tetrakis(μ-pyrene-1-carboxylato)dicopper(Cu—Cu), [Cu2(C17H9O2)4(C2H6OS)2] or [Cu2(pyr-COO−)4(DMSO)2] (1), and bis(dimethylformamide)tetrakis(μ-pyrene-1-carboxylato)dicopper(Cu—Cu), [Cu2(C17H9O2)4(C3H7NO)2] or [Cu2(pyr-COO−)4(DMF)2] (2) (pyr = pyrene), were synthesized from the reaction of pyrene-1-carboxylic acid, copper(II) nitrate and triethylamine from solvents DMSO and DMF, respectively. While 1 crystallized in the space group P\overline{1}, the crystal structure of 2 is in space group P21/n. The Cu atoms have octahedral geometries, with four oxygen atoms from carboxylate pyrene ligands occupying the equatorial positions, a solvent molecule coordinating at one of the axial positions, and a Cu...Cu contact in the opposite position. The packing in the crystal structures exhibits π–π stacking interactions and short contacts through the solvent molecules. The Hirshfeld surfaces and two-dimensional fingerprint plots were generated for both compounds to better understand the intermolecular interactions and the contribution of heteroatoms from the solvent ligands to the crystal packing. In addition, a Cu2+/Cu1+ quasi-reversible redox process was identified for compound 2 using cyclic voltammetry that accounts for a diffusion-controlled electron-donation process to the Cu dimer.

Mechanically deformable polymeric semiconductors are a key material for fabricating flexible organic thin‐film transistors (FOTFTs)—the building block of electronic circuits and wearable electronic devices. However, for many π‐conjugated polymers achieving mechanical deformability and efficient charge transport remains challenging. Here the effects of polymer backbone bending stiffness and film microstructure on mechanical flexibility and charge transport are investigated via experimental and computational methods for a series of electron‐transporting naphthalene diimide (NDI) polymers having differing extents of π‐conjugation. The results show that replacing increasing amounts of the π‐conjugated comonomer dithienylvinylene (TVT) with the π‐nonconjugated comonomer dithienylethane (TET) in the backbone of the fully π‐conjugated polymeric semiconductor, PNDI‐TVT100 (yielding polymeric series PNDI‐TVTx, 100 ≥ x ≥ 0), lowers backbone rigidity, degree of texturing, and π–π stacking interactions between NDI moieties. Importantly, this comonomer substitution increases the mechanical robustness of PNDI‐TVTx while retaining efficient charge transport. Thus, reducing the TVT content of PNDI‐TVTx suppresses film crack formation and dramatically stabilizes the field‐effect electron mobility upon bending (e.g., 2 mm over 2000 bending cycles). This work provides a route to tune π–π stacking in π‐conjugated polymers while simultaneously promoting mechanical flexibility and retaining good carrier mobility in FOTFTs. [ABSTRACT FROM AUTHOR]

In the emerging aqueous zinc ion batteries (AZIBs), proton (H+) with the smallest molar mass and fast (de)coordination kinetics is considered as the most ideal charge carrier compared with Zn2+ counterpart, however, searching for new hosting materials for H+ storage is still at its infancy. Herein, redox‐active hydrogen‐bonded organic frameworks (HOFs) assembled from diaminotriazine moiety decorated hexaazatrinnphthalene (HOF‐HATN) are for the first time developed as the stable cathode hosting material for boosting H+ storage in AZIBs. The unique integration of hydrogen‐bonding networks and strong π‐π stacking endow it rapid Grotthuss proton conduction, stable supramolecular structure and inclined H+ storage. As a consequence, HOF‐HATN displays a high capacity (320 mAh g−1 at 0.05 A g−1) and robust cyclability of (>10000 cycles at 5 A g−1) based on three‐step cation coordination storage. These findings get insight into the proton transport and storage behavior in HOFs and provide the molecular engineering strategy for constructing well‐defined cathode hosting materials for rechargeable aqueous batteries. [ABSTRACT FROM AUTHOR]

A C‐3 symmetric imine functional nonpolymeric low molecular weight gelator is prepared using microwave assisted Schiff base reaction. The synthesized molecule forms a hydrogel at 5 wt% under slightly acidic pH. The material was characterized using an inversion tube test, thermogravimetric analysis (TGA), powder X‐ray diffraction (PXRD) and FT‐IR spectroscopy. Rheological studies show the material forms a strong hydrogel with formation of nanofibrils supported by field‐emission scanning electron microscopy (FE‐SEM). To the best of our knowledge this is the first example of imine based trigonal low molecular weight hydrogelator reported. [ABSTRACT FROM AUTHOR]

Perylene diimides (PDI) are workhorses in the field of organic electronics, owing to their appealing n‐semiconducting properties. Optimization of their performances is widely pursued by bay‐atom substitution and diverse imide functionalization. Bulk solids and thin‐films of these species crystallize in a variety of stacking configurations, depending on the geometry of the stable conformation of the polyaromatic core. We here demonstrate that 1,7‐dibromo‐substituted perylene diimides, PDI(H2Br2), possessing a heavily twisted conformation in the gas phase, in solution and in the solids, can be easily flattened in the solid state into centrosymmetric molecules if the polyaromatic cores form π–π stabilized chains. This is achieved by using axial residues with low stereochemical hindrance, as guaranteed by a single CH2/NH spacer directly linked to the imide function. Structural powder diffraction and DFT calculations on four newly designed species of the PDI(H2Br2) class coherently show that, thanks to the flexibility of the N−X−Ar link (X=CH2/NH), flat cores are indeed obtained by overcoming the interconversion barrier between twisted atropoisomers, of only 26.5 kJ mol−1. This strategy may then be useful to induce "anomalously flat" polyaromatic cores of different kinds (substituted acenes/rylenes) in the solid state, towards suitable crystal packing and orbital interactions for improved electronic performances. [ABSTRACT FROM AUTHOR]

In the title complex, [Ru(C10H8N2)2(C6H6N2O)(H2O)](CF3SO3)2, the central RuII atom is sixfold coordinated by two bidentate 2,2′-bipyridine, an isonicotinamide ligand, and a water molecule in a distorted octahedral environment with trifluoromethanesulfonate ions completing the outer coordination sphere of the complex. Hydrogen bonding involving the water molecule and weak π–π stacking interactions between the pyridyl rings in adjacent molecules contribute to the alignment of the complexes in columns parallel to the c axis.

The reaction of 8-aminoquinoline, zinc chloride and hydrochloric acid in ethanol yielded the title salt, (C9H10N2)[ZnCl4], which consists of a planar 8-azaniumylquinolinium dication and a tetrahedral tetrachlorozincate dianion. The 8-aminoquinoline moiety is protonated at both the amino and the ring N atoms. In the crystal, the cations and anions are connected by intermolecular N—H...Cl and C—H...Cl hydrogen bonds, forming sheets parallel to (001). Adjacent sheets are linked through π–π interactions involving the pyridine and arene rings of the 8-azaniumylquinolinium dication. Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H...Cl (48.1%), H...H (19.9%), H...C/C...H (14.3%) (involving the cations) and H...Cl (82.6%) (involving the anions) interactions.

π–π stacking are omnipresent interactions, crucial in many areas of chemistry, and often studied using quantum chemical methods. Here, we report a simple and computationally efficient method of estimating the binding energies of stacked polycyclic aromatic hydrocarbons based on steered molecular dynamics. This method leverages the force field parameters for accurate calculation. The presented results show good agreement with those obtained through DFT at the ωB97X-D3/cc-pVQZ level of theory. It is demonstrated that this force field-driven SMD method can be applied to other aromatic molecules, allowing insight into the complexity of the stacking interactions and, more importantly, reporting π–π stacking energy values with reasonable precision.

Comprehensive Summary: Ultra‐narrow bandgap (ultra‐NBG) small molecule acceptors (SMAs) show great potential in organic solar cells (OSCs) due to the extended near‐infrared (NIR) absorption. In this work, a synergetic alkoxy side‐chain and chlorine‐contained end group strategy is employed to achieve A‐DA'D‐A type ultra‐NBG SMAs by introducing alkoxy chains with oxygen atom at the second position into the thiophene β position as well as replacing the F atoms with Cl atoms in the end group. As a result, the heptacyclic BZO‐4F shows a redshifted absorption onset (960 nm) compared with Y11 (932 nm) without oxygen atoms in the side chains. Then, the fluorinated end groups are substituted with the chlorinated ones to synthesize BZO‐4Cl. The absorption onset of BZO‐4Cl is further redshifted to 990 nm, corresponding to an optical ultra‐NBG of 1.25 eV. When blending with the polymer donor PBDB‐T, the binary devices based on PBDB‐T:BZO‐4F and PBDB‐T:BZO‐4Cl deliver power conversion efficiencies (PCEs) over 12%. Furthermore, ternary devices with the addition of BZ4F‐O‐1 into PBDB‐T:BZO‐4Cl system achieve the optimal PCE of 15.51%. This work proposes a synergetic alkoxy side‐chain and chlorine‐contained end group strategy to achieve A‐DA'D‐A type ultra‐NBG SMAs, which is important for future molecular design. [ABSTRACT FROM AUTHOR]

This study systematically investigates the molecular structure and electronic properties of 2-methoxy-4,6-diphenylnicotinonitrile, employing X-ray diffraction (XRD) and sophisticated computational methodologies. XRD findings validate the compound's orthorhombic crystallization in the P21212 space group, composed of a pyridine core flanked by two phenyl rings. Utilizing the three-dimensional Hirshfeld surface, the research decodes the molecule's spatial attributes, further supported by exhaustive statistical assessments. Key interactions, such as π–π stacking and H⋯X contacts, are spotlighted, underscoring their role in the crystal's inherent stability and characteristics. Energy framework computations and density functional theory (DFT) analyses elucidate the prevailing forces in the crystal and reveal geometric optimization facets and molecular reactivity descriptors. Emphasis is given to the exploration of frontier molecular orbitals (FMOs), aromaticity, and π–π stacking capacities. The research culminates in distinguishing electron density distributions, aromatic nuances, and potential reactivity hotspots, providing a holistic view of the compound's structural and electronic landscape. Concurrently, molecular docking investigates its interaction with the lipoprotein-associated phospholipase A2 protein. Notably, the compound showcases significant interactions with the protein's active site. Molecular dynamics simulations reveal the compound's influence on protein stability and flexibility. Although the molecule exhibits strong inhibitory potential against Lp-PLA2, its drug development prospects face challenges related to solubility and interactions with drug transport proteins. [ABSTRACT FROM AUTHOR]

[Display omitted] Herein, ultra dispersed and stably suspended nanodiamonds (NDs) were demonstrated to have a high load capacity, sustained release, and ability to serve as a biocompatible vehicle for delivery anticancer drugs. NDs with size of 50–100 nm exhibited good biocompatibility in normal human liver (L-02) cells. In particular, 50 nm ND not only promoted the noticeable proliferation of the L-02 cells but also can effectively inhibited the migration of human liver carcinoma (HepG2) cells. The gambogic acid-loaded nanodiamond (ND/GA) complex assembled by π–π stacking exhibits ultrasensitive and apparent suppression efficiency on the proliferation of HepG2 cells through high internalization and less efflux compared to free GA. More importantly, the ND/GA system can significantly increase the intracellular reactive oxygen species (ROS) levels in HepG2 cells and thus induce the cell apoptosis. The increase in intracellular ROS levels causes damage to the mitochondrial membrane potential (MMP) and activates cysteinyl aspartate specific proteinase 3 (Caspase-3) and cysteinyl aspartate specific proteinase 9 (Caspase-9), which leads to the occurrence of apoptosis. In vivo experiments also confirmed that the ND/GA complex has a much higher anti-tumor capability than free GA. Thus, the current ND/GA system is promising for cancer therapy. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Intramolecular interactions are fundamental for the unique structures and outstanding properties of metallofullerenes. However, how the internal metal species interplay with the cluster configuration inside oxide clusterfullerenes remains poorly understood. Herein, we successfully captured two oxide clusterfullerenes with different metals, namely, Lu2O@C82 and Er2O@C82, to elucidate the role of metal species in tuning cluster configuration. The two molecules have been fully characterized by mass spectrometry, Vis‐NIR absorption spectroscopy, cyclic voltammetry, and single‐crystal X‐ray diffraction. Crystallographic data show that their isomeric cages were both determined as Cs(6)‐C82. Further structural analysis reveals that the Lu1‐O‐Lu2 angle value in Lu2O@Cs(6)‐C82 is much larger than the Er1‐O‐Er2 angle value in Er2O@Cs(6)‐C82, indicating that the configuration of the endohedral oxide clusters is flexible and dependent on the metal ion radius. Additionally, electrochemical studies suggest that the variation in entrapped metal species causes differences in redox properties, for which the first oxidation and first reduction potentials of Lu2O@Cs(6)‐C82 are shifted positively and negatively, respectively, compared to the counterparts of Er2O@Cs(6)‐C82, resulting in a larger electrochemical band‐gap. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Intramolecular interactions are fundamental for the unique structures and outstanding properties of metallofullerenes. However, how the internal metal species interplay with the cluster configuration inside oxide clusterfullerenes remains poorly understood. Herein, we successfully captured two oxide clusterfullerenes with different metals, namely, Lu2O@C82 and Er2O@C82, to elucidate the role of metal species in tuning cluster configuration. The two molecules have been fully characterized by mass spectrometry, Vis‐NIR absorption spectroscopy, cyclic voltammetry, and single‐crystal X‐ray diffraction. Crystallographic data show that their isomeric cages were both determined as Cs(6)‐C82. Further structural analysis reveals that the Lu1‐O‐Lu2 angle value in Lu2O@Cs(6)‐C82 is much larger than the Er1‐O‐Er2 angle value in Er2O@Cs(6)‐C82, indicating that the configuration of the endohedral oxide clusters is flexible and dependent on the metal ion radius. Additionally, electrochemical studies suggest that the variation in entrapped metal species causes differences in redox properties, for which the first oxidation and first reduction potentials of Lu2O@Cs(6)‐C82 are shifted positively and negatively, respectively, compared to the counterparts of Er2O@Cs(6)‐C82, resulting in a larger electrochemical band‐gap. [ABSTRACT FROM AUTHOR]

Thermoplastic polyimides (PIs) with shape memory potential have received growing attention in recent years. In this work, high-performance thermoplastic PIs were fabricated by introducing PIs with chain rigidity (r-PI) into PI with chain flexibility (f-PI). The influences of molecular chain entanglement and π-π interactions on their thermomechanical and shape memory properties were investigated. The degree of molecular chain entanglement was quantitively characterized based on dynamic mechanical analysis (DMA). The π-π interactions were investigated in detail by X-ray diffraction (XRD) and UV-Vis spectroscopy. It was found that the entanglement density increased and π-π interactions became stronger with the introduction of r-PI into f-PI, leading to the improvement of shape recovery. Moreover, a broad and increased glass transition temperature (Tg) was achieved, endowing the PIs with multiple shape memory properties. The synergistic effects of increased entanglement density and enhanced π-π interactions were beneficial to regulating interchain interactions and thereby achieving high shape memory performance of the PIs. [ABSTRACT FROM AUTHOR]

The reaction of 8-aminoquinoline, zinc chloride and hydrochloric acid in ethanol yielded the title salt, (C9H10N2)[ZnCl4], which consists of a planar 8-azaniumylquinolinium dication and a tetrahedral tetrachlorozincate dianion. The 8-aminoquinoline moiety is protonated at both the amino and the ring N atoms. In the crystal, the cations and anions are connected by intermolecular N--H...Cl and C--H...Cl hydrogen bonds, forming sheets parallel to (001). Adjacent sheets are linked through π-π interactions involving the pyridine and arene rings of the 8-azaniumylquinolinium dication. Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H...Cl (48.1%), H...H (19.9%), H...C/C...H (14.3%) (involving the cations) and H...Cl (82.6%) (involving the anions) interactions. [ABSTRACT FROM AUTHOR]

The molecular and crystal structures of the title compound, [Cu2I2(C18H12N2)2], were examined by single-crystal X-ray diffraction and Hirshfeld surface analysis. The Cu atom is coordinated in a distorted tetrahedral geometry by two N atoms from the 2,2′-biquinoline ligands and the two μ2-bridging iodide ligands. The molecules are in contact via π–π-stacking interactions. Hirshfeld surface analysis showed that the most important contributions to the intermolecular interactions are H...H (39.7%), H...I/I...H (17.8%), C...H/H...C (17.5%), C...C (16.5%), N...C/C...N (3.9%) and N...H/H...N (3.5%).

The new Lewis acid–base adducts of general formula X(nad)B←NC5H4-C5H4N→B(nad)X [nad = 1,8-O2C10H6, X = C6H5 (2c), 3,4,5-F3-C6H2 (2d)] were synthesized in high yields via reactions of 1,8-dihydroxy naphthalene [nadH2] and 4,4′-bipyridine with the aryl boronic acids C6H5B(OH)2 and 3,4,5-F3-C6H2B(OH)2, respectively, and structurally characterized by multi-nuclear NMR spectroscopy and SCXRD. Self-assembled H-shaped Lewis acid–base adduct 2d proved to be effective in forming thermally stable host–guest complexes, 2d × solvent, with aromatic hydrocarbon solvents such as benzene, toluene, mesitylene, aniline, and m-, p-, and o-xylene. Crystallographic analysis of these solvent adducts revealed host–guest interactions to primarily occur via π···π contacts between the 4,4′-bipyridyl linker and the aromatic solvents, resulting in the formation of 1:1 and 1:2 host–guest complexes. Thermogravimetric analysis of the isolated complexes 2d × solvent revealed their high thermal stability with peak temperatures associated with the loss of solvent ranging from 122 to 147 °C. 2d, when self-assembled in an equimolar mixture of m-, p-, and o-xylene (1:1:1), preferentially binds to o-xylene. Collectively, these results demonstrate the ability of 1,8-dihydroxy naphthalene to serve as an effective building block in the selective self-assembly to supramolecular aggregates through dative covalent N→B bonds. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: The brightness of fluorescent agents directly determines the imaging performance as required. Among various fluorophores, small organic species are promising given its exact purity/composition and excellent processibility. However, chromophores with planar geometry may suffer from the undesirable aggregation‐caused quenching (ACQ) phenomenon. Encouragingly, luminogens showing aggregation‐induced emission (AIE) features are preferable as the aggregates which are the most common used state. In this review, we mainly focus on the strategies employed for boosting the brightness of AIE‐active luminogens (AIEgens). From molecule to morphology levels, approaches that regulate electronic transition processes of the molecule or the packing extent of aggregates in order to confine molecular motion, reduce π‐π stacking, disrupt fluorophore‐water interactions, etc., are presented. In the end, the current challenges and perspectives are briefly discussed. We anticipate that this review will stimulate new insights and more efforts for the advancement of ultrabright AIEgens. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: The brightness of fluorescent agents directly determines the imaging performance as required. Among various fluorophores, small organic species are promising given its exact purity/composition and excellent processibility. However, chromophores with planar geometry may suffer from the undesirable aggregation‐caused quenching (ACQ) phenomenon. Encouragingly, luminogens showing aggregation‐induced emission (AIE) features are preferable as the aggregates which are the most common used state. In this review, we mainly focus on the strategies employed for boosting the brightness of AIE‐active luminogens (AIEgens). From molecule to morphology levels, approaches that regulate electronic transition processes of the molecule or the packing extent of aggregates in order to confine molecular motion, reduce π‐π stacking, disrupt fluorophore‐water interactions, etc., are presented. In the end, the current challenges and perspectives are briefly discussed. We anticipate that this review will stimulate new insights and more efforts for the advancement of ultrabright AIEgens. [ABSTRACT FROM AUTHOR]

A new two-dimensional (2D) metal–organic complex, [Pb(L)(I)(sba)0.5]2 (1, L = 2-(2,4-difluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, H2sba = suberic acid), was synthesized under hydrothermal conditions. The single-crystal X-ray analysis indicates that the asymmetric unit of complex 1 has a distorted [:PbIN2O2] octahedral geometry. It is further extended by two π–π stacking interactions and N–H⋯O hydrogen bonding to form and stabilize 2D supramolecular layer.

Advanced elastomers are increasingly used in emerging areas, for example, flexible electronics and devices, and these real‐world applications often require elastomers to be stretchable, tough and fire safe. However, to date there are few successes in achieving such a performance portfolio due to their different governing mechanisms. Herein, a stretchable, supertough, and self‐extinguishing polyurethane elastomers by introducing dynamic π–π stacking motifs and phosphorus‐containing moieties are reported. The resultant elastomer shows a large break strain of ≈2260% and a record‐high toughness (ca. 460 MJ m−3), which arises from its dynamic microphase‐separated microstructure resulting in increased entropic elasticity, and strain‐hardening at large strains. The elastomer also exhibits a self‐extinguishing ability thanks to the presence of both phosphorus‐containing units and π–π stacking interactions. Its promising applications as a reliable yet recyclable substrate for strain sensors are demonstrated. The work will help to expedite next‐generation sustainable advanced elastomers for flexible electronics and devices applications. [ABSTRACT FROM AUTHOR]

The unavoidable iodine loss in the perovskite layer is closely related to carrier non‐radiative and device degradation. During the post‐annealing process, the fragile PbI bond is easy to break, leading to the formation of iodine vacancies and inducing stress‐driven structure collapse. Herein, a PbI6 octahedra stabilization strategy via building robust grain boundary modification networks is developed. The introduction of conjugated structure into amides can significantly enhance their anchoring ability with PbI units, while the π–π stacking effect of benzamide enables a passivation network with polymer‐like effect. This is well evidenced by the excellent properties in eliminated iodine loss and stabilized perovskite lattice. Therefore, benzamide modification not only transform the perovskite films from n‐type to p‐type by suppressing the iodine vacancy‐doping effect, but also reduces defect density, ultimately bringing the perovskite layer longer carrier diffusion length and better charge injection efficiency. Finally, the benzamide modified devices realize both high power conversion efficiency of 24.78% and excellent operating stability. Of particular note, the module efficiency with 14 cm2 active area is over 21%. [ABSTRACT FROM AUTHOR]

Dyes are a class of hazardous chemicals that can cause harm to the environment and life on earth. However, it remains a huge challenge for the effective removal of the dyes. Herein, a new metal-organic capsule {[Cu(L)(bpy)(H2O)]·H2O}n (1) was synthesised by (4,4'-(((1,3,4-thiadiazole-2,5-diyl)bis(sulfanediyl))bis (methylene)) dibenzoic acid, 2,2'-bipyridine and CuCl2∙2 H2O under solvothermal condition. Interestingly, two inversion asymmetric units are connected by O-H···O and O-H···N to form a centrosymmetric capsule with cavity. The intermolecular interactions were further quantitatively analysed and visualised by the CrystalExplorer 17.5. Notably, complex 1 can effectively adsorb methylene blue (MB), and the adsorption performance is linearly correlated with MB concentration. When the concentration of MB was increased from 10 to 50 mg∙L−1, the adsorption performance of 1 was increased from 17.68 to 66.79 mg∙g−1, while reduced the MB removal efficiency from 88.4% to 66.4%. The adsorption process is suitable for the pseudo-second-order and the Langmuir model. Furthermore, complex 1 showed the good recyclability and stability for at least five runs. [ABSTRACT FROM AUTHOR]

Lacking high‐performance nonlinear optical (NLO) materials limits the applications to opto‐electronic devices. In this work, a strategy of self‐assembling driven by π‐π stacking is proposed to design high‐performance NLO materials. Here, the third‐order NLO responses of two carbon‐based fuller‐rylenes dimers (Fuller‐PMI and Fuller‐PDI) are theoretically studied. The results mainly highlight the following points: (1) these two dimers are in good thermodynamic and kinetic stability, and the interaction energies of Fuller‐PMI and Fuller‐PDI dimers have reached to −63.50 kcal/mol and −68.18 kcal/mol, respectively; (2) the ratios of the static second order hyperpolarizability (γiiiiFF, i∈{x, y, z}) between the dimer and the monomer are γxxxxFFdimerγxxxxFFmonomer = 5.5, γyyyyFFdimerγyyyyFFmonomer = 1.2 and γzzzzFFdimerγzzzzFFmonomer = 1.2 for Fuller‐PMI, γxxxxFFdimerγxxxxFFmonomer = 1.1, γyyyyFFdimerγyyyyFFmonomer =1.4 and γzzzzFFdimerγzzzzFFmonomer = 4.2 for Fuller‐PDI. These results demonstrate that the self‐assembling driven by π‐π stacking is an effective strategy for designing high‐performance NLO materials. [ABSTRACT FROM AUTHOR]

The purpose of this research work is to synthesize near-infrared dye–sensitized nanocomposites with core–shell nanostructures of titanium dioxide/reduced nanographene oxide (TiO2/r-NGO) to be an effective photocatalyst for effluent degradation followed hydrogen generation under visible light irradiation. The generation of hydrogen using photocatalysts has been intensely researched for the effective utilization of hydrogen in a controlled way. The mechanistic pathway for both hydrogen generation and effluent degradation utilizes the electrons generated through photoexcitation during dye sensitization. For this reason, the squaraine dyes were synthesized by the C-H-direct arylation method and made the nanocomposites with self-assembled core/shell nanocomposites (r-NGOT), where TiO2 serves as the core and r-NGO as the shell. Due to the lack of anchoring groups, VJ-Q was only adsorbed on the surface of r-NGOT through π-π stacking, which is confirmed by Fourier transformed-infrared spectroscopy, X-ray photoelectron spectroscopy, high resolution-transmission electron microscopy, and electron energy loss spectroscopy. The optical absorption spectra of VJ-Q/r-NGOT nanocomposites measured with diffuse reflectance UV/visible absorption spectroscopy covers the whole range of visible light wavelengths up to 800 nm. During the photocatalytic activity, VJ-Q/r-NGOT/Pt followed a ligand-to-metal-charge transfer (LMCT) type mechanism for the electron transfer to the core–shell nanostructure. This mechanistic pathway is utilized for the effluent dye degradation followed hydrogen generation through water splitting. The photocatalytic efficiency of the nanocomposite with adsorbed dye is superior to that of dye-TiO2 due to the large surface area provided by r-NGO and the prevention of dye aggregation. The work is significant due to the limited research works that are carried under dye-sensitized nanocomposites that have been utilized for both dye degradation and hydrogen generation. [ABSTRACT FROM AUTHOR]