Short Bond Research Articles

The Challenging World of Simple Inorganic Rings: Revisiting Roesky's Ketone and Roesky's Sulfoxide.

The surprising differences between the experimental solid-state and calculated gas-phase structures of 5-oxo-1,3,2,4-dithiadiazole (Roesky's ketone, 1) and 1-oxo-1,2,4,3,5-trithiadiazole (Roesky's sulfoxide, 2), identified and studied in a series of papers published between 2004 and 2010 but then never satisfactorily explained, have been revisited, making use of the more advanced computational possibilities currently available. The previous calculations' considerable overestimations of the C-S and S-S bond lengths in 1 and 2, respectively, have been partly explained based on the results of periodic calculations and the application of Valence Bond (VB) Theory. In the case of 1, the crystal environment appears to stabilize a structure with a highly polarized C=O bond, which features a C-S bond with considerable double-bond character - an effect which does not exist for the isolated molecule - explaining the much shorter bond in the solid state. For 2, a similar conclusion can be drawn for the S-S distance. For both compounds, though, packing effects are not the sole source of the differences: the inability of Density Functional Theory (DFT) to properly deal with the electronic structures of these apparently simple main-group systems remains a contributing factor.

Five-coordinated bis-dioxolene cobalt complexes with triphenylphosphine

Three novel five-coordinated bis-dioxolene cobalt complexes with triphenylphosphine were synthesized. Complexes differ by dioxolene ligands: 3,6-di-tert-butylcyclohexa-3,5-diene-1,2-dione (complex 1), 5,8-di-tert-butyl-2,3-dihydro-1,4-ethanoquinoxaline-6,7-dione (complex 2), 3,6-di-tert-butyl-4-methoxycyclohexa-3,5-diene-1,2-dione (complex 3). The geometry of the inner coordination core of all compounds is close to square pyramidal. The base of the pyramid is formed by oxygen atoms of the dioxolene ligands whereas phosphine occupies the apical position. The planes of dioxolenes are slightly bent relative to each other. The magnetic moment values at low temperatures correspond to one unpaired electron per molecule for all complexes. In the complex containing a methoxy group in the dioxolene ligand (3), an increase in the magnetic moment is observed upon heating above 250 K, which indicates the appearance of a fraction of molecules with a higher spin multiplicity. A slight elongation of the Co-O, Co-P distances and shortening of the CO bonds is observed at 353 K. DFT calculations using the TPSSh functional correctly reproduce geometries of the complexes as well as their electronic absorption and vibrational spectra. DFT predicts the doublet-state complexes to possess the lowest enthalpies. Gibbs free energy of sextet complex 3 in solution is lower than that of its doublet state. This agrees well with the experimental electronic absorption spectra. On the basis of TD DFT calculations, a strong NIR absorption band in the spectra of low-spin 1 and 2 is assigned to the transition involving charge transfer from cobalt to the dioxolene and PPh3 ligands (MLCT). The doublet molecules can be described by the (↑SQ—)(Co3+)(Cat2—) ↔ (Cat2—)(Co3+)(↑SQ—) resonance structures. The sextet state in all three systems represents the (↑SQ—)(↑↑↑Co2+)(PPh3)(↑SQ—) bis-semiquinonate complex of high-spin Co(II). On the basis of the conventional description the doublet → sextet transition in complexes can be interpreted as a VT/SCO transformation. The electron density analysis of the doublet → sextet transition in the 1 and 3 molecules reveals areas of both increase and decrease in the charge density near the Co and O atoms.

Does judicial reform affect firms’ short-term debt for long-term use? Evidence from China

ABSTRACT Under the background of the misplacement of time and space in the trial judicial reform in China, this paper constructs a difference-in-difference model with multiple time periods to systematically investigate the influence of judicial reform on the short-term debt for long-term use of Chinese listed companies and its economic consequences. The research results show that, compared with the companies not affected by the judicial reform pilot, the short debt long ratio of the companies affected by the judicial reform pilot increased by 8.76% on average, and this phenomenon is more obvious in non-state-owned enterprises, asset-light enterprises, small enterprises and enterprises with unified leadership. In addition, it is found that the judicial reform and firms’ short-term debt for long-term use increase the risk of corporate bankruptcy. The results help to clarify the mystery of debt maturity structure in China, and provide new ideas and evidence for alleviating the long-term use of corporate short bonds, improving the mismatch of investment and financing maturity and preventing systemic financial risks.

Synthesis of Single Crystal Li2NpO4 and Li4NpO5 from Aqueous Lithium Hydroxide Solutions under Mild Hydrothermal Conditions.

The ternary oxides, Li2NpO4 and Li4NpO5, were synthesized under mild hydrothermal conditions using concentrated LiOH solutions containing NpO2(NO3)2. The reactions resulted in the formation of single crystals of both compounds, enabling the determination of their single crystal structures for the first time. Exploration of the synthetic phase space demonstrates that the resulting neptunate phases are dependent on the concentration of LiOH, transitioning from Li2NpO4, containing a typical octahedral neptunyl geometry with two shorter Np≡O bonds, at lower LiOH concentrations to Li4NpO5 with two long and four short Np-O bonds under saturated solution conditions. Reactions exploring the same synthetic conditions are also reported for uranyl(VI) for comparison. Raman spectra of the compounds were collected and analyzed to evaluate the Np-O bonding in these compounds.

The Crystal Structure of Pb10(PO4)6O Revisited: The Evidence of Superstructure

The crystal structure of Pb10(PO4)6O, the proposed matrix for the potential room-temperature superconductor LK-99, Pb10−xCux(PO4)6O (x = 0.9–1.0), has been reinvestigated via single-crystal X-ray diffraction using crystals prepared by Merker and Wondratschek (Z. Anorg. Allg. Chem. 1960, 306, 25–29). The crystal structure is trigonal, P3¯, a = 9.8109(6), c = 14.8403(12) Å, V = 1237.06(15), R1 = 0.0413 using 3456 unique observed reflections. The crystal structure of Pb10(PO4)6O is a superstructure with regard to the ‘standard’ P63/m apatite structure type. The doubling of the c parameter is induced through the ordering of the split sites of ‘additional’ O’ atoms within the structure channels running parallel to the c axis and centered at (00z). The O’ atoms form short bonds to the Pb1 atoms, resulting in splitting the Pb1 site into two, Pb1A and Pb1B. The structural distortions are further transmitted to the Pb phosphate framework formed by four Pb2 sites and PO4 groups. The structure data previously reported by Krivovichev and Burns (Z. Kristallogr. 2003, 218, 357–365) may either correspond to the Pb10(PO4)6Ox(OH)2−2x (x ~ 0.4) member of the Pb10(PO4)6O—Pb10(PO4)6(OH)2 solid solution series, or to the high-temperature polymorph of Pb10(PO4)6O (with the phase with doubled c parameter being the low-temperature polymorph).

Regioselective N-sulfonylation of 3-(methylthio)-1H-1,2,4-triazol-5-amine: Spectroscopic, thermal, crystal structure, and anticancer studies

We described a regioselective synthesis of two 1-(arylsulfonyl)-1H-1,2,4-triazol-5-amines 17 with good yields through a triethylamine-mediated N-sulfonylation reaction of 1H-1,2,4-triazol-5-amine 15 with arylsulfonyl chlorides 16 in dichloromethane at ambient temperature for 3 h. The N-heterocyclic sulfonamides 17 were characterized by spectroscopy, mass spectrometry, thermal analysis, and single crystal X-ray diffraction (SC-XRD). The SC-XRD analysis showed that compounds 17a and 17b have layered molecular structures, which are assembled through short hydrogen bonds involving N-H‧‧‧N, N-H‧‧‧O, C-H‧‧‧O, and C-H‧‧‧π, and interconnected by π‧‧‧π stacking interactions. For the two triazoles, electrostatic forces are the dominant attracting force within the molecular sheets, while dispersion forces play a more predominant role between the sheets. The packing arrangements were studied by crystallographic analysis and complementarily through computational calculations. Finally, these sulfonamides 17a and 17b demonstrated the most promising in vitro anticancer activity against the SNB-75 and UO-31 cell lines associated with the central nervous system and renal cancer, exhibiting moderate growth inhibition percentages of 18.7 % and 27.2 %, respectively.

Experimental and numerical simulation of pull-out response in textile-reinforced concrete

Textile-reinforced concrete (TRC) is a construction material that uses continuous fibres such as carbon to create a lightweight and durable structural system. Even though TRC possesses vast possibilities in terms of its usage, identification of bond-slip behaviour at the material interface is one of the limitations that need to be addressed. Based on the literature, there are difficulties in determining the bond-slip relationship both experimentally and numerically, creating inconsistency in the results. This study aims to determine the bond-slip relation of TRC through pullout tests and validated through finite element analysis to replicate the actual bond-slip behaviour at the interface. The bond characteristics of TRC were assessed using a double-sided pullout test setup with different bond lengths of textile, namely 20 mm, 30 mm, 40 mm, 50 mm, and 60 mm. It was noticed that in short bond specimens (20 mm, 30 mm, and 40 mm), the phenomena of pullout failure were due to weakened bond at the interface until pre-peak, followed by complete loss of adhesive bond due to debonding of fibre. However, for the specimens with longer bond lengths (50 mm and 60 mm), rupture of the textile leading to a sudden loss of bond capacity was observed. Additionally, the general fibre pullout phenomenon curve was used to explain the debonding process. Using a calibrated tri-linear bond-slip interface relation, the numerical model was developed to simulate the pull-out response of fibre. The numerical model was able to reproduce experimental results, including maximum load, post-peak behaviour, and interfacial slip. The difference of maximum shear stress between pull-out tests and numerical modelling was within 2 % while the slip difference was between 4 and 31 % for different bond lengths. However, for longer bond lengths, the fibre failure mode was due to pullout instead of rupture, unlike the experimental results.

Development of an Iron(II) Complex Exhibiting Thermal- and Photoinduced Double Proton-Transfer-Coupled Spin Transition in a Short Hydrogen Bond.

Multiple proton transfer (PT) controllable by external stimuli plays a crucial role in fundamental chemistry, biological activity, and material science. However, in crystalline systems, controlling multiple PT, which results in a distinct protonation state, remains challenging. In this study, we developed a novel tridentate ligand and iron(II) complex with a short hydrogen bond (HB) that exhibits a PT-coupled spin transition (PCST). Single-crystal X-ray and neutron diffraction measurements revealed that the positions of the two protons in the complex can be controlled by temperature and photoirradiation based on the thermal- and photoinduced PCST. The obtained results suggest that designing molecules that form short HBs is a promising approach for developing multiple PT systems in crystals.

Examining the Effect of Cu and Mn Dopants on the Structure of Zinc Blende ZnS Nanopowders.

It is known that doping zinc sulfide (ZnS) nanoparticles with Mn or Cu ions significantly affects their luminescent properties. Herein, we investigated how dopant atoms are incorporated into the structure of ZnS using X-ray diffraction and multi-edge X-ray absorption spectroscopy. The observed broadening of the X-ray diffraction patterns indicates an average crystallite size of about 6 nm. By analyzing the Zn, Mn, and Cu K-edge extended X-ray absorption fine structure (EXAFS) spectra using the reverse Monte Carlo method, we were able to determine the relaxations of the local environments around the dopants. Our findings suggested that upon the substitution of Zn by Mn or Cu ions, there is a shortening of the Cu-S bonds by 0.08 Å, whereas the Mn-S bonds exhibited lengthening by 0.07 Å. These experimental results were further confirmed by first-principles density functional theory calculations, which explained the increase in the Mn-S bond lengths due to the high-spin state of Mn2+ ions.

Chemical features and machine learning assisted predictions of protein-ligand short hydrogen bonds

There are continuous efforts to elucidate the structure and biological functions of short hydrogen bonds (SHBs), whose donor and acceptor heteroatoms reside more than 0.3 Å closer than the sum of their van der Waals radii. In this work, we evaluate 1070 atomic-resolution protein structures and characterize the common chemical features of SHBs formed between the side chains of amino acids and small molecule ligands. We then develop a machine learning assisted prediction of protein-ligand SHBs (MAPSHB-Ligand) model and reveal that the types of amino acids and ligand functional groups as well as the sequence of neighboring residues are essential factors that determine the class of protein-ligand hydrogen bonds. The MAPSHB-Ligand model and its implementation on our web server enable the effective identification of protein-ligand SHBs in proteins, which will facilitate the design of biomolecules and ligands that exploit these close contacts for enhanced functions.

The Characterization of Mechanical and Chemical Properties of Recycled Styrofoam Waste Employing Extrusion Process

<p><em>Styrofoam waste is a polystyrene plastic-based waste in the form of foam with low density. Scavengers or recyclers are not interested in receiving styrofoam waste because of its light density which makes it ineffective in transportation and storage. Styrofoam waste can actually be converted into solid polystyrene products through a thermal-extrusion process but data regarding the optimum operating temperature and the characteristics of the resulting solid polystyrene products are not yet available. The purpose of this study was to investigate the properties of solid polystyrene products resulting from recycled styrofoam waste and determine the optimum temperature of the thermal-extrusion treatment process to be compared with the characteristics of the original polystyrene based on the results of tensile and impact tests. In this study, the processing was carried out using the thermal-extrusion method; Styrofoam is melted and extruded into a mold to produce polystyrene solids. The research was carried out with variations in extrusion temperature at 180°C, 200°C, and 220°C. The polystyrene solids are then molded into tensile and impact test specimens by injection molding. The results showed that the optimal extrusion temperature was 200°C with tensile and impact strength values of 27.55 MPa and 1,069 j/m2, respectively. Compared to the original polystyrene, the tensile strength value is 25.3% lower and the impact strength value is 29.5% lower. The decrease in the tensile and impact strength values is due to the shortening of the molecular bonds in the recycled polystyrene during the thermal-extrusion treatment process. Even though the tensile strength and impact are still lower, the use of styrofoam waste using the thermal-extrusion method has the potential to be developed at the production and commercialization stage because the resulting product has good economic value and can also reduce the use of original polystyrene and at the same time can solve the problem of styrofoam waste.</em></p>

Advanced interfacial phase change material: Structurally confined and interfacially extended superlattice

Interfacial Phase Change Memory (iPCM) retrench unnecessary power consumption due to wasted heat generated during phase change by reducing unnecessary entropic loss. In this study, an advanced iPCM (GeTe/Ti-Sb2Te3 Superlattice) is synthesized by doping Ti into Sb2Te3. Structural analysis and density functional theory (DFT) calculations confirm that bonding distortion and structurally well-confined layers contribute to improve phase change properties in iPCM. Ti-Sb2Te3 acts as an effective thermal barrier to localize the generated heat inside active region, which leads to reduction of switching energy. Since Ge-Te bonds adjacent to short and strong Ti-Te bonds are more elongated than the bonds near Sb-Te, it is easier for Ge atoms to break the bond with Te due to strengthened Peierls distortions (Rlong/Rshort) during phase change process. Properties of advanced iPCM (cycling endurance, write speed/energy) exceed previous records. Moreover, well-confined multi-level states are obtained with advanced iPCM, showing potential as a neuromorphic memory. Our work paves the way for designing superlattice based PCM by controlling confinement layers.

X-ray Spectroscopic Study of the Electronic Structure of a Trigonal High-Spin Fe(IV)═O Complex Modeling Non-Heme Enzyme Intermediates and Their Reactivity.

Fe K-edge X-ray absorption spectroscopy (XAS) has long been used for the study of high-valent iron intermediates in biological and artificial catalysts. 4p-mixing into the 3d orbitals complicates the pre-edge analysis but when correctly understood via 1s2p resonant inelastic X-ray scattering and Fe L-edge XAS, it enables deeper insight into the geometric structure and correlates with the electronic structure and reactivity. This study shows that in addition to the 4p-mixing into the 3dz2 orbital due to the short iron-oxo bond, the loss of inversion in the equatorial plane leads to 4p mixing into the 3dx2-y2,xy, providing structural insight and allowing the distinction of 6- vs 5-coordinate active sites as shown through application to the Fe(IV)═O intermediate of taurine dioxygenase. Combined with O K-edge XAS, this study gives an unprecedented experimental insight into the electronic structure of Fe(IV)═O active sites and their selectivity for reactivity enabled by the π-pathway involving the 3dxz/yz orbitals. Finally, the large effect of spin polarization is experimentally assigned in the pre-edge (i.e., the α/β splitting) and found to be better modeled by multiplet simulations rather than by commonly used time-dependent density functional theory.

Predicting the effects of doping and pressure on the structural, mechanical and electronic properties of B12P2*

Based on the first-principles calculations, the effects of doping and pressure on the B12P2 have been investigated and discussed systematically. The calculated formation enthalpy and phonon dispersion curves show that the pure and N-doped B12P2 are structurally stable. Mechanical properties demonstrated that the Vickers hardness of B12P2 was successfully improved (from 38.1 GPa to 43.4 GPa) by partially replacing P with N, which due to the short bond length between B and N atoms and can also be well understood by the band structure around the Fermi level. In addition, the calculated B/G and Poisson's ratio ν reveal that the pure and N-doped B12P2 are intrinsically brittleness and strongly prone to ductility under pressure, especially the pure B12P2 undergoes a brittle-to-ductile transition when the pressure is above 93.5 GPa, which is beneficial to the application of mechanical materials under extreme conditions. In addition, the visual elastic anisotropy also shows an enhanced trend under pressure. Finally, the electronic structure calculations indicate that the N-doped B12P2 becomes a wide-band-gap semiconductor under pressure, which is an attractive candidate for high voltage/high power devices.

Resistance profiles for the investigational neuraminidase inhibitor AV5080 in influenza A and B viruses

Neuraminidase inhibitors (NAIs) are recommended for influenza treatment and prevention worldwide. The most widely prescribed NAI is oral oseltamivir, while inhaled zanamivir is less commonly used. Using phenotypic neuraminidase (NA) enzymatic assays and molecular modeling approaches, we examined the ability of the investigational orally-dosed NAI AV5080 to inhibit viruses of the influenza A(H1N1)pdm09, A(H3N2), A(H5N1), and A(H7N9) subtypes and the influenza B/Victoria- and B/Yamagata-lineages containing NA substitutions conferring oseltamivir or zanamivir resistance including: NA-R292K, NA-E119G/V, NA-H274Y, NA-I122L/N, and NA-R150K. Broadly, AV5080 showed enhanced in vitro efficacy when compared with oseltamivir and/or zanamivir. Reduced AV5080 inhibition was determined for influenza A viruses with NA-E119G and NA-R292K, and for B/Victoria-lineage viruses with NA-I122N/L and B/Yamagata-lineage virus with NA-R150K. Molecular modeling suggested loss of the short hydrogen bond to the carboxyl group of AV5080 affected inhibition of NA-R292K viruses, whereas loss of the salt bridge with the guanidine group of AV5080 affected inhibition of NA-E119G. The resistance profiles and predicted binding modes of AV5080 and zanamivir are most similar, but dissimilar to those of oseltamivir, in part because of a guanidine moiety compensatory binding effect. Overall, our data suggests that AV5080 is a promising orally-dosed NAI that exhibited similar or superior in vitro efficacy against viruses with reduced or highly reduced inhibition phenotypes with respect to currently approved NAIs.

Tetrel bond in the triphenyltin(IV) chloride-cyclo-hexyl-diphenyl-phosphane oxide (1/1) cocrystal.

The single-crystal X-ray diffraction structure of the title compound, [SnCl(C6H5)3]·C18H21OP, is reported. The 1:1 cocrystal features a short and directional tetrel bond between tin and oxygen. The tin-oxygen distance is 2.346 (4) Å, representing 62% of the sum of the van der Waals radii of Sn and O. The Cl-Sn⋯O angle is 174.0 (1)° and this nearly linear arrangement is consistent with a tetrel bond formed via a σ-hole opposite the tin-chlorine covalent bond. Some weak C-H⋯Cl inter-actions are noted between adjacent mol-ecules.

Hydrogen storage properties of Mg0.10Ti0.30V0.25Zr0.10Nb0.25 lightweight high entropy alloy: A theoretical study

In the past several years, Mg-based high entropy alloys (HEAs) have attracted great attention in high gravimetric hydrogen storage capacity. In this work, the hydrogen storage properties of Mg0.10Ti0.30V0.25Zr0.10Nb0.25 HEA are investigated by first-principles calculations. With increasing hydrogen concentration, the structural stability of BCC and FCC hydrides decreases and increases, respectively. By comparing the lattice constants, number of hydrogenation-induced abnormal short hydrogen-hydrogen bonds and radial distribution functions of BCC and FCC hydrides, it is found that the hydrogen accommodation ability of BCC phase is weaker than that of FCC phase, and a BCC to FCC phase transformation occurs during hydrogenation process. Further total energy calculations suggest that the threshold hydrogen content of phase transformation for Mg0.10Ti0.30V0.25Zr0.10Nb0.25 is around H/M = 1.16. By phonon spectra calculation, the maximum gravimetric hydrogen storage capacity of Mg0.10Ti0.30V0.25Zr0.10Nb0.25 is predicated to be as high as 3.16 wt%, demonstrating that Mg0.10Ti0.30V0.25Zr0.10Nb0.25 HEA is a potential hydrogen storage material.

In-situ Raman unveiled Nb-O-bond-dependency selectivity for methanol electro-oxidation at high current density

Selective methanol oxidation reaction (MOR) to value-added formate can maximize the energy utilization by replacing the high onset-potential and sluggish oxygen evolution reaction. However, to date, only first-row 3d transition metal oxides exhibit the capacity of selective MOR, motivating the design of new kinds of electrocatalysts to further enhance the performance. Here we develop amorphous Nb2O5 as an efficient electrocatalyst, for the first time, for selective MOR to formate, with a low operating potential of 1.47 V vs. RHE to achieve the industry-relevant current densities (>100 mA cm−2) with a formate Faradaic efficiency of ∼100 %. We demonstrate, via operando Raman measurements, that this superior electrochemical MOR capacity originates from the in-situ induced short Nb-O bonds from the amorphous structure. Besides, the interface between amorphous Nb2O5 and nickel foam could also faciltate the MOR. This work may provide insights for designing novel transition metal oxides as efficient catalysts for selective MOR.

Mechanical Seed Mechanism to Facilitate Homogeneous Li Metal Growth

AbstractAn intriguing mechanical seed (MS) concept that modulates (in)homogeneous Li metal growth is proposed based on an in‐depth understanding of its fundamental mechanism using unified atomistic computations. A large dataset of thermodynamic energies for Li disordered phase decouples the dual‐body interactions into three components: i) crystal‐like, ii) long, and iii) short bonds of Li─Li based on machine learning assisted by density function theory calculations. The contributions of these dual‐body interactions offer a mechanical factor for controlling the disordered‐ordered phase transition during electrochemical deposition. Macroscopic molecular dynamics simulations systematically construct the core–shell sphere and cross‐sectional models to reinforce the MS premise. The former reveals that the lower energy level of disordered phase under the moderate compression causes a slow phase kinetics, whereas the strain‐free mode exhibits a relatively fast transition. In addition, the cross‐sectional model exhibits a smooth surface landscape for the strain‐optimized case. These observations are attributed to the surface area evolutions depending on the MS conditions and elucidate the dynamic atomic displacements near the grain boundary from a local structural perspective. The proposed mechanical design concept facilitates uniform Li growth and is expected to be a global parameter in harnessing the full potential of Li metal batteries.

Experimental charge density and topological analysis of tetraaquabis(hydrogenmaleato)nickel(II): a comparison with Hirshfeld atom refinement.

Experimental charge density analysis is conducted on the coordination compound tetraaquabis(hydrogenmaleato)nickel(II), which exhibits a short intramolecular hydrogen bond. Through topological analysis, the nature of Ni-O bonds is concluded to be intermediate between ionic and covalent, but mainly presenting an ionic character, while the short hydrogen bond is classified as covalent in nature. The compound was also analysed after Hirshfeld atom refinement performed using NoSpherA2. A topological analysis was conducted on the molecular wavefunction and the results are compared with those obtained from experiment. In general, there is good agreement between the refinements, and the chemical bonds involving H atoms are in better agreement with what is expected from neutron data after HAR than they are after multipole refinement.