Unveiling the Nature and Strength of Selenium-Centered Chalcogen Bonds in Binary Complexes of SeO2 with Oxygen-/Sulfur-Containing Lewis Bases: Insights from Theoretical Calculations.

Among various non-covalent interactions, selenium-centered chalcogen bonds (SeChBs) have garnered considerable attention in recent years as a result of their important contributions to crystal engineering, organocatalysis, molecular recognition, materials science, and biological systems. Herein, we systematically investigated π-hole-type Se∙∙∙O/S ChBs in the binary complexes of SeO2 with a series of O-/S-containing Lewis bases by means of high-level ab initio computations. The results demonstrate that there exists an attractive interaction between the Se atom of SeO2 and the O/S atom of Lewis bases. The interaction energies computed at the MP2/aug-cc-pVTZ level range from -4.68 kcal/mol to -10.83 kcal/mol for the Se∙∙∙O chalcogen-bonded complexes and vary between -3.53 kcal/mol and -13.77 kcal/mol for the Se∙∙∙S chalcogen-bonded complexes. The Se∙∙∙O/S ChBs exhibit a relatively short binding distance in comparison to the sum of the van der Waals radii of two chalcogen atoms. The Se∙∙∙O/S ChBs in all of the studied complexes show significant strength and a closed-shell nature, with a partially covalent character in most cases. Furthermore, the strength of these Se∙∙∙O/S ChBs generally surpasses that of the C/O-H∙∙∙O hydrogen bonds within the same complex. It should be noted that additional C/O-H∙∙∙O interactions have a large effect on the geometric structures and strength of Se∙∙∙O/S ChBs. Two subunits are connected together mainly via the orbital interaction between the lone pair of O/S atoms in the Lewis bases and the BD*(OSe) anti-bonding orbital of SeO2, except for the SeO2∙∙∙HCSOH complex. The electrostatic component emerges as the largest attractive contributor for stabilizing the examined complexes, with significant contributions from induction and dispersion components as well.

Halogen Bond via an Electrophilic π-Hole on Halogen in Molecules: Does It Exist?

This study reveals a new non-covalent interaction called a π-hole halogen bond, which is directional and potentially non-linear compared to its sister analog (σ-hole halogen bond). A π-hole is shown here to be observed on the surface of halogen in halogenated molecules, which can be tempered to display the aptness to form a π-hole halogen bond with a series of electron density-rich sites (Lewis bases) hosted individually by 32 other partner molecules. The [MP2/aug-cc-pVTZ] level characteristics of the π-hole halogen bonds in 33 binary complexes obtained from the charge density approaches (quantum theory of intramolecular atoms, molecular electrostatic surface potential, independent gradient model (IGM-δginter)), intermolecular geometries and energies, and second-order hyperconjugative charge transfer analyses are discussed, which are similar to other non-covalent interactions. That a π-hole can be observed on halogen in halogenated molecules is substantiated by experimentally reported crystals documented in the Cambridge Crystal Structure Database. The importance of the π-hole halogen bond in the design and growth of chemical systems in synthetic chemistry, crystallography, and crystal engineering is yet to be fully explicated.

Conformation-Associated C···dz2-PtII Tetrel Bonding: The Case of Cyclometallated Platinum(II) Complex with 4-Cyanopyridyl Urea Ligand.

The nucleophilic addition of 3-(4-cyanopyridin-2-yl)-1,1-dimethylurea (1) to cis-[Pt(CNXyl)2Cl2] (2) gave a new cyclometallated compound 3. It was characterized by NMR spectroscopy (1H, 13C, 195Pt) and high-resolution mass spectrometry, as well as crystallized to obtain two crystalline forms (3 and 3·2MeCN), whose structures were determined by X-ray diffraction. In the crystalline structure of 3, two conformers (3A and 3B) were identified, while the structure 3·2MeCN had only one conformer 3A. The conformers differed by orientation of the N,N-dimethylcarbamoyl moiety relative to the metallacycle plane. In both crystals 3 and 3·2MeCN, the molecules of the Pt(II) complex are associated into supramolecular dimers, either {3A}2 or {3B}2, via stacking interactions between the planes of two metal centers, which are additionally supported by hydrogen bonding. The theoretical consideration, utilizing a number of computational approaches, demonstrates that the C···dz2(Pt) interaction makes a significant contribution in the total stacking forces in the geometrically optimized dimer [3A]2 and reveals the dz2(Pt)→π*(PyCN) charge transfer (CT). The presence of such CT process allowed for marking the C···Pt contact as a new example of a rare studied phenomenon, namely, tetrel bonding, in which the metal site acts as a Lewis base (an acceptor of noncovalent interaction).

Leveraging the photocatalytic Cr (VI) reduction by an IRMOF-3@NH2-MIL-101 (Fe) heterostructure based on interfacial Lewis acid-base interaction.

A strategy to enhance the photocatalytic performance of metal-organic framework (MOF) based systems for the efficient elimination of Cr(VI) ions from polluted water under visible light irradiation has been developed by constructing MOF@MOF heterojunctions. Specifically, IRMOF-3 was grown in situ around NH2-MIL-101(Fe) based on interfacial Lewis acid-base interaction using 2-aminoterephthalic acid (ATA) as a linker, resulting in the formation of a MOF@MOF heterojunction, designated as IRMOF-3@NH2-MIL-101(Fe). In comparison to individual MOFs, the IRMOF-3@NH2-MIL-101(Fe) heterojunction exhibited a significantly higher photocatalytic reduction efficiency for Cr(VI), achieving a reduction of 95.98% within 120 min under visible-light irradiation. This performance surpasses that of individual MOFs and most reported photocatalysts. Additionally, the mechanism underlying Cr(VI) reduction by IRMOF-3@NH2-MIL-101(Fe) was comprehensively elucidated by analyzing optoelectronic properties, energy band structure, and structural results. It is worth noting that this study represents the first documented instance of photocatalytic Cr(VI) reduction utilizing IRMOF-3 and its interaction with NH2-MIL-101(Fe). The MOF@MOF photocatalyst, leveraging the synergistic effects of its various components, holds great promise for efficiently removing harmful pollutants from water and finds significant potential applications in environmental remediation.

Lewis acid/base mediated deep eutectic solvents intensify lignocellulose fractionation to facilitate enzymatic hydrolysis and lignin nanosphere preparation.

In this work, Lewis acids (FeCl3, AlCl3) and bases (Na2CO3, Na2SO3) were incorporated into a neutral deep eutectic solvent (DES, choline chloride/glycerin) to intensify the lignocellulose fractionation. The efficiency of fractionation in terms of the maximum delignification rate (89.7 %) and well-pleasing cellulose saccharification (100 %) could be achieved by the Lewis acid-mediated DES. An in-depth insight of the evolution of lignin structure revealed that Lewis acid-mediated DES could cleave the ß-O-4 linkages efficiently to achieve a high yield lignin fragments. Meanwhile, the lignin fragments with the enhanced amphiphilic properties facilitate the preparation of lignin nanospheres (LNSs) via the self-assembly process. The resultant LNSs extracted by Lewis acid-mediated DES exhibited an excellent thermal stability, and enhanced antibacterial capacity, which were associated with the phenolic OH content. However, the extracted lignin by Lewis base-mediated DES was mainly attributed to the cleavage of lignin-carbohydrate complexes bond, especially the lignin-carbohydrate ester bond, which retained more ether bonds and a relatively complete structure. This study illuminated the different mechanisms of lignin extraction and the structural evolution of lignin from Lewis acid/base-mediated DES, and provided guidance to select suitable fractionation techniques for upgrading the downstream products.

A promising sensing platform for explosive markers: Zeolite-like metal-organic framework based monolithic composite as a case study.

Preconcentration for on-site detection or subsequent determination is a promising technique for selective sensing explosive markers at low concentrations. Here, we report divinylbenzene monolithic polymer in its blank form (neat-DVB) and as a composite incorporated with sodalite topology zeolite-like metal-organic frameworks (3-ZMOF@DVB), as a sensitive, selective, and cost-effective porous preconcentrator for aliphatic nitroalkanes in the vapor phase as explosive markers at infinite dilution. The developed materials were fabricated as 18 cm gas chromatography (GC) monolithic capillary columns to study their separation performance of nitroalkane mixture and the subsequent physicochemical study of adsorption using the inverse gas chromatography (IGC) technique. A strong preconcentration effect was indicated by a specific retention volume adsorption/desorption ratio equal to 3 for nitromethane on the neat-DVB monolith host-guest interaction, and a 14% higher ratio was observed using the 3-ZMOF@DVB monolithic composite despite the low percentage of 0.7 wt.% of sod-ZMOF added. Furthermore, Incorporating ZMOF resulted in a higher percentage of micropores, increasing the degree of freedom more than bringing stronger adsorption and entropic-driven interaction more than enthalpic. The specific free energy of adsorption (ΔGS) values increased for polar probes and nitroalkanes, denoting that adding ZMOFs earned the DVB monolithic matrix a more specific character. Afterward, Lewis acid-base properties were calculated, estimating the electron acceptor (KA) and electron donor (KB) constants. The neat-DVB was found to have a Lewis basic character with KB/KA = 7.71, and the 3-ZMOF@DVB had a less Lewis basic character with KB/KA = 3.82. An increased electron-accepting nature can be directly related to incorporating sod-ZMOF into the DVB monolithic matrix. This work considers the initial step in presenting a portable explosives detector or preconcentrating explosive markers trace prior to more sophisticated analysis. Additionally, the IGC technique allows for understanding the factors that led to the superior adsorption of nitroalkanes for the developed materials.

C∙∙∙O and Si∙∙∙O Tetrel Bonds: Substituent Effects and Transfer of the SiF3 Group.

The tetrel bond (TB) between 1,2-benzisothiazol-3-one-2-TF3-1,1-dioxide (T = C, Si) and the O atom of pyridine-1-oxide (PO) and its derivatives (PO-X, X = H, NO2, CN, F, CH3, OH, OCH3, NH2, and Li) is examined by quantum chemical means. The Si∙∙∙O TB is quite strong, with interaction energies approaching a maximum of nearly 70 kcal/mol, while the C∙∙∙O TB is an order of magnitude weaker, with interaction energies between 2.0 and 2.6 kcal/mol. An electron-withdrawing substituent on the Lewis base weakens this TB, while an electron-donating group has the opposite effect. The SiF3 group transfers roughly halfway between the N of the acid and the O of the base without the aid of cooperative effects from a third entity.

Enhancing the Performance of Perovskite Solar Cells by Introducing 4-(Trifluoromethyl)-1H-imidazole Passivation Agents.

Defects in perovskite films are one of the main factors that affect the efficiency and stability of halide perovskite solar cells (PSCs). Uncoordinated ions (such as Pb2+, I-) act as trap states, causing the undesirable non-radiative recombination of photogenerated carriers. The formation of Lewis acid-base adducts in perovskite directly involves the crystallization process, which can effectively passivate defects. In this work, 4-(trifluoromethyl)-1H-imidazole (THI) was introduced into the perovskite precursor solution as a passivation agent. THI is a typical amphoteric compound that exhibits a strong Lewis base property due to its lone pair electrons. It coordinates with Lewis acid Pb2+, leading to the reduction in defect density and increase in crystallinity of perovskite films. Finally, the power conversion efficiency (PCE) of PSC increased from 16.49% to 18.97% due to the simultaneous enhancement of open-circuit voltage (VOC), short circuit current density (JSC) and fill factor (FF). After 30 days of storage, the PCE of the 0.16 THI PSC was maintained at 61.9% of its initial value, which was 44.3% for the control device. The working mechanism of THI was investigated. This work provides an attractive alternative method to passivate the defects in perovskite.

Functionalized Metal-Organic Framework for Selective Fluorometric Detection of Sodium Dodecyl Sulfate and Vitamin B12 Using MOF@Cotton Composites and Lewis Base-Catalyzed Condensation Reaction.

A zirconium(IV)-based metal-organic framework (MOF) fluorophore containing the 2,5-diaminoterephthalic acid (H2BDC-(NH)2) linker was synthesized and characterized. The physicochemically stable, porous (SBET = 504 m2 g-1) MOF (1') exhibited selective and sensitive fluorescence turn-on behavior toward the sodium dodecyl sulfate (SDS) surfactant and turn-off response toward vitamin B12. This is the first ever reported MOF-based dual optical sensor of SDS and vitamin B12. Other competitive analytes did not interfere in the detection of both the analytes. Along with the lowest ever reported limit of detection (LOD) values (LOD for SDS = 108 nM and LOD for vitamin B12 = 45.3 nM), 1' displayed short response time for SDS (50 s) and vitamin B12 (5 s) detection. The MOF was able to detect SDS in various real water samples and vitamin B12 in various bio-fluids (urine and serum) and pH media. A MOF-coated cotton composite was fabricated, which displayed a visible color change under UV light even after treating it with a nanomolar concentration of both the analytes. The sensor displayed excellent reusability up to five cycles of sensing. Various experimental outcomes evidenced that the electrostatic interaction between the -NH2 groups of the linker and the -SO3- group of SDS is the possible reason for the selective SDS sensing. For vitamin B12, the energy transfer from the probe to vitamin B12 resulted in fluorescence quenching. In addition, the catalytic performance of 1' was investigated in the condensation reaction between benzaldehyde derivatives with cyanoacetamide with high yields in ethanol at 70 °C. The solid was used for three cycles with no decrease in its activity and selectivity. PXRD and FESEM analysis before and after the reaction suggested the retention of the crystallinity of 1', thus indicating catalyst stability.

Dynamic Metalloporphyrin-Based [2]Rotaxane Molecular Shuttles Stimulated by Neutral Lewis Base and Anion Coordination.

A series of dynamic metalloporphyrin [2]rotaxane molecular shuttles comprising of bis-functionalised Zn(II) porphyrin axle and pyridyl functionalised macrocycle components are prepared in high yield via active metal template synthetic methodology. Extensive variable temperature 1 H NMR and quantitative UV-Vis spectroscopic titration studies demonstrate dynamic macrocycle translocation is governed by an inter-component co-ordination interaction between the macrocycle pyridyl and axle Zn(II) metalloporphyrin, which serves to bias a 'resting state' co-conformation. The dynamic shuttling behaviour of the interlocked structures is dramatically inhibited by the addition of a neutral Lewis base such as pyridine, but can also be tuned via post-synthetic rotaxane demetallation of the porphyrin axle core to give free-base, or upon subsequent metallation, Ni(II) [2]rotaxane analogues. Importantly, the Lewis acidic Zn(II) porphyrin axle component is also capable of coordinating anions which induces mechanical bond shuttling behaviour resulting in a novel optical sensing response.

Mesoporous MgO enriched in Lewis base sites as effective catalysts for efficient CO2 capture.

Capturing CO2 has become increasingly important. However, wide industrial applications of conventional CO2 capture technologies are limited by their slow CO2 sorption and desorption kinetics. Accordingly, this research is designed to overcome the challenge by synthesizing mesoporous MgO nanoparticles (MgO-NPs) with a new method that uses PEG 1500 as a soft template. MgO surface structure is nonstoichiometric due to its distinctive shape; the abundant Lewis base sites provided by oxygen vacancies promote CO2 capture. Adding 2 wt % MgO-NPs to 20 wt % monoethanolamine (MEA) can increase the breakthrough time (the time with 90% CO2 capturing efficiency) by ∼3000% and can increase the CO2 absorption capacity within the breakthrough time by ∼3660%. The data suggest that MgO-NPs can accelerate the rate and increase CO2 desorption capacity by up to ∼8740% and ∼2290% at 90 °C, respectively. Also, the excellent stability of the system within 50 cycles is verified. These findings demonstrate a new strategy to innovate MEA absorbents currently widely used in commercial post-combustion CO2 capture plants.

Insight into the Varying Reactivity of Different Catalysts for CO2 Cycloaddition into Styrene Oxide: An Experimental and DFT Study.

The cycloaddition of CO2 into epoxides to form cyclic carbonates is a highly sought-after reaction for its potential to both reduce and use CO2, which is a greenhouse gas. In this paper, we present experimental and theoretical studies and a mechanistic approach for three catalytic systems. First, as Lewis base catalysts, imidazole and its derivatives, then as a Lewis acid catalyst, ZnI2 alone, and after that, the combined system of ZnI2 and imidazole. In the former, we aimed to discover the reasons for the varied reactivities of five Lewis base catalysts. Furthermore, we succeeded in reproducing the experimental results and trends using DFT. To add, we emphasized the importance of non-covalent interactions and their role in reactivity. In our case, the presence of a hydrogen bond was a key factor in decreasing the reactivity of some catalysts, thus leading to lower conversion rates. Finally, mechanistically understanding this 100% atom economy reaction can aid experimental chemists in designing better and more efficient catalytic systems.

Realizing Scalable Nano-SiO2-Aerogel-Reinforced Composite Polymer Electrolytes with High Ionic Conductivity via Rheology-Tuning UV Polymerization.

Polymer electrolytes for lithium metal batteries have aroused widespread interest because of their flexibility and excellent processability. However, the low ambient ionic conductivity and conventional fabrication process hinder their large-scale application. Herein, a novel polyethylene-oxide-based composite polymer electrolyte is designed and fabricated by introducing nano-SiO2 aerogel as an inorganic filler. The Lewis acid-base interaction between SiO2 and anions from Li salts facilitates the dissociation of Li+. Moreover, the SiO2 interacts with ether oxygen (EO) groups, which weakens the interaction between Li+ and EO groups. This synergistic effect produces more free Li+ in the electrolyte. Additionally, the facile rheology-tuning UV polymerization method achieves continuous coating and has potential for scalable fabrication. The composite polymer electrolyte exhibits high ambient ionic conductivity (0.68 mS cm-1) and mechanical properties (e.g., the elastic modulus of 150 MPa). Stable lithium plating/stripping for 1400 h in Li//Li symmetrical cells at 0.1 mA cm-2 is achieved. Furthermore, LiFePO4//Li full cells deliver superior discharge capacity (153 mAh g-1 at 0.5 C) and cycling stability (with a retention rate of 92.3% at 0.5 C after 250 cycles) at ambient temperature. This work provides a promising strategy for polymer-based lithium metal batteries.

Size Regulation of Polydopamine Nanoparticles by Boronic Acid and Lewis Base.

Size regulation of polydopamine nanoparticles (PDA NPs) is vital to melanin-inspired materials. The general strategy usually focuses on tuning of the reaction parameters which could affect the dopamine (DA) monomer polymerization process, such as pH, temperature, monomer concentration, etc. The reaction between boronic acids and catechols to form boronic esters has been widely applied in many fields, but little attention has been paid in the size regulation of PDA NPs. Here, it is speculated that the fine size regulation of PDA NPs can be directly achieved by using boronic acids and Lewis base molecules. It is found that these issues could indeed significantly affect the stability of the boronic esters formed by boronic acids and DA, which may further inhibit the monomer polymerization kinetics and tune the particle size of the resulting PDA NPs. It is also found that the several intrinsic properties of PDA NPs such as the free radical scavenging ability, UV spectral absorption, photothermal behavior, and structural color all change with the particle size. It is believed that this work can provide new opportunities for fabricating melanin-inspired PDA NPs with well controlled size and properties.

Interfacial superassembly of flower-like NiMn-LDH@poly-l-lysine composites for selective electrochemical sensing of tryptophan.

Development of sensitive, selective, and facile electrochemical analytical approaches to monitor tryptophan in different samples is of high significance. For such approaches, efficient electrodes play the key role. Herein, a NiMn-layered double hydroxide (LDH)@poly-l-lysine (PLL) composite has been prepared through in-situ electro-polymerization and further utilized to monitor tryptophan in medicament and biological systems. The as-synthesized NiMn-LDH@PLL composite is highly stable and features a flower-like morphology. It is found that the electron transfer rate of NiMn-LDH@PLL is greatly improved due to the introduction of PLL. The existing Lewis acid-base interaction between LDH and PLL contributes to the increase of unsaturated metal sites and endows this heterojunction composite with high electrocatalytic activity. Especially, the NiMn-LDH (2:1)@PLL composite displays much improved electrochemical response toward tryptophan sensing. This is due to reasonable balance between the outstanding electrocatalytic ability of nickel and the conductivity improvement caused by manganese species. On the other hand, the coordination promotion between NiMn-LDH and PLL is also conducive to improve the sensitivity of electrochemical response. The fabricated sensor exhibits wide linear response in the concentration ranges of 0.1-40 µM and 40-130 µM for tryptophan detection, along with a low detection limit of 52.7 nM. It further displays a high anti-interference ability for tryptophan monitoring even in the presence of other coexistent amino acids and small-sized biological molecules. This study provides a new way to employ LDHs as brilliant sensing platform to ensemble electrochemical sensors for the monitoring of biomolecules.

Phosphorus and oxygen co-doped carbon particles based on almond shells with hydrothermal and microwave irradiation process for adsorption of lead (II) and cadmium (II).

In this study, the production of activated carbon based on almond shells by microwave heating with KOH activation and then the modification of activated carbon with phosphorus and oxygen as a result of hydrothermal heating with phosphoric acid were carried out to increase the Cd(II) and Pb(II) adsorption efficiency. The resulting materials were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric/differential thermal analyzer (TG-DTA), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and nitrogen adsorption. Adsorption performance, kinetics and thermodynamics of phosphorus, and oxygen-doped activated carbons were evaluated. The results showed that the adsorption of both Cd(II) and Pb(II) on phosphorus and oxygen-doped activated carbons obeyed the Langmuir isotherm and pseudo-second-order kinetics. The adsorption capacity values (Qm) obtained from the Langmuir isotherm for Cd(II) and Pb(II) adsorption were 185.18 mg/g and 54.64 mg/g, respectively. At the same time, the adsorption mechanism of Pb(II) and Cd(II) on the respective adsorbents was evaluated. As a result of phosphorus and oxygen atoms, Lewis base sites on carbon atoms and Lewis acid sites on phosphorus atoms are likely to form on the surface. These Lewis base sites can act as important active sites in adsorption reactions, especially of positively charged Pb(II) and Cd(II) ions.

A butterfly shaped Eu4(OH)2 cluster-based luminescent metal-organic framework with Lewis basic triazole sites demonstrating turn off sensing in the presence of organic amines.

The effective detection of organic amines is particularly important for environmental protection and human health. Herein, according to hard and soft acid base theory, a novel three-dimensional (3D) butterfly shaped Eu4(OH)2 cluster-based metal-organic framework with Lewis basic triazole sites, {[Eu4(taip)4(ox)(OH)2(H2O)4]·3H2O}n (1) (H2taip = 5-(1,2,4-triazol-1-yl) isophthalic acid, H2ox = oxalic acid), was successfully synthesized under solvothermal conditions, and was characterized by single crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, infrared spectroscopy and thermogravimetric analysis. Structural analysis reveals that compound 1 is a 3D net constructed from butterfly shaped Eu4(OH)2 clusters and contains isosceles triangular channels with dimensions of 8.84 × 8.84 × 8.63 Å3, which shows an unprecedented 8-connected topology with a Schläfli symbol {36·418·53·6}. Fluorescence experiments of compound 1 show sensitive luminescence quenching responses to organic amines such as diethylamine (DEA), trimethylamine (TMA), triethylamine (TEA), ethylenediamine (EDA) and aniline, and the quenching constants (KSV) decrease in the following order: EDA > DEA > TMA > TEA > aniline. The fluorescence quenching responses may be attributed to the energy gap between the LUMO energy values of H2taip and organic amines, which hinders the transfer of excited state energy to the emission state of Eu3+ and results in luminescence quenching. The fluorescence lifetimes of compound 1 in ethanol and organic anilines indicate that the fluorescence recognition process of organic amines was static.

Significantly Enhanced Carbon Dioxide Selective Adsorption via Gradual Acylamide Truncation in MOFs: Experimental and Theoretical Research.

A gradual amide truncation strategy was presented to tune the pore chemistry and CO2 capture performance of a series of tetracarboxylate-based Cu-MOFs. These MOFs exhibited a high density of Lewis basic sites (LBSs) and open metal sites and were prepared with the goal to enhance CO2 selective adsorption capacity. [Cu2(L1)(H2O)2]n (NJU-Bai42: NJU-Bai for Nanjing University Bai's group), [Cu2(L2) (H2O)2]n (NJU-Bai17), and [Cu2(L3)(H2O)2]n (NTUniv-60: NTUniv for Nantong University) were synthesized, and we observed that the CO2 adsorption capacities and MOF structures were impacted by subtle changes in ligands. Interestingly, although the NTUniv-60 was decorated with the least LBSs in these three MOFs, its CO2 adsorption capacity reached 270 (53.0 wt %) and 164 (32.2 wt %) cm3 g-1 at 273 and 296 K under 1 bar, respectively, which is the highest data reported for MOFs under similar conditions. From the grand canonical Monte Carlo (GCMC) simulation, the cooperative interactions between the CO2 molecules within the shuttle-shaped cages of NTUniv-60 could potentially explain why the CO2 uptake is high in this material.

Effects of Lewis Basicity and Acidity on σ-Hole Interactions in Carbon-Bearing Complexes: A Comparative Ab Initio Study.

The effects of Lewis basicity and acidity on σ-hole interactions were investigated using two sets of carbon-containing complexes. In Set I, the effect of Lewis basicity was studied by substituting the X3/X atom(s) of the NC-C6H2-X3 and NCX Lewis bases (LB) with F, Cl, Br, or I. In Set II, the W-C-F3 and F-C-X3 (where X and W = F, Cl, Br, and I) molecules were utilized as Lewis acid (LA) centers. Concerning the Lewis basicity effect, higher negative interaction energies (Eint) were observed for the F-C-F3∙∙∙NC-C6H2-X3 complexes compared with the F-C-F3∙∙∙NCX analogs. Moreover, significant Eint was recorded for Set I complexes, along with decreasing the electron-withdrawing power of the X3/X atom(s). Among Set I complexes, the highest negative Eint was ascribed to the F-C-F3∙∙∙NC-C6H2-I3 complex with a value of -1.23 kcal/mol. For Set II complexes, Eint values of F-C-X3 bearing complexes were noted within the -1.05 to -2.08 kcal/mol scope, while they ranged from -0.82 to -1.20 kcal/mol for the W-C-F3 analogs. However, Vs,max quantities exhibited higher values in the case of W-C-F3 molecules compared with F-C-X3; preferable negative Eint were ascribed to the F-C-X3 bearing complexes. These findings were delineated as a consequence of the promoted contributions of the X3 substituents. Dispersion forces (Edisp) were identified as the dominant forces for these interactions. The obtained results provide a foundation for fields such as crystal engineering and supramolecular chemistry studies that focus on understanding the characteristics of carbon-bearing complexes.

Bifunctional Lewis Base Catalyzed Asymmetric N-Allylic Alkylation of 2-Hydroxypyridines.

A chiral Lewis base catalyzed enantioselective N-allylic alkylation of 2-hydroxypyridines and MBH carbonates is documented, affording a convenient access to N-alkylated 2-pyridones with up to 99% ee and 99% yield. Experimental and computational studies have revealed that the strong hydrogen bond interaction between the chiral Lewis base catalyst and 2-hydroxypyridines plays a crucial role in this reaction for the reactivity, chemoselectivity, and enantioselectivity.