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In the process of handling and storage of radioactive actinides it is essential to selectively sequester the minor actinides, such as Am and Cm, through a competitive complexation process. Herein we computationally designed two core modified ligands (L21− and L3) through systematic oxygen substitution at the NH sites of dipyriamethyrin (L1_2H), a hexadentate expanded porphyrin, and studied their competitive complexation towards trivalent actinides (An = Am/Cm) from their trichlorides using density functional theory (DFT). We observed shorter An–N bonds and longer An–O bonds in complexes based on core modified ligands (L21− and L3). The An–Cl bond length increases with increasing axial coordination number (i.e., from L12− to L3) to accommodate the ligands. All the bonds were identified to be electrostatic in nature. L12− exhibits shorter bonds and larger bond orders on complexing with Am than with Cm. On moving from complexes of L21− to L3, the An–N bond lengths are shortened, while An–O bond lengths become larger. Between the complexes of Am and Cm, there is marginal difference in their bond distances with L21− and L3. Charge analysis shows ligand to metal charge transfer during coordination, with back-donation from An to N/O and Cl. The calculated spin-density analysis indicates that An remains in its trivalent oxidation state on complexation, while orbital occupation analysis shows that the 5f and 6d orbitals are involved in bonding; this was confirmed by molecular orbital (MO) analysis that shows the complexes of L21− and L3 to exhibit higher degeneracy in their overlapping MOs. Further, the energy decomposition analysis (EDA) confirms that all ionic bonds are primarily due to electrostatic contributions, where the orbital contributions increase from L12− to L3 complexes and maximum covalency was observed in Cm complexes due to the energy matching between the 5f orbitals of Cm and the 2p orbitals of N and Cl, compared to Am. To confirm the competitiveness in the complexation of the ligand towards Am vs. Cm, the thermodynamic parameters were analysed for the ligand and metal substitution reactions. L12− shows more affinity towards Am than Cm, while L21− and L3 prefer Cm. [ABSTRACT FROM AUTHOR]

This study investigates the influence of ligand charge on transition energies in a series of CuN2S2 complexes based on dithiocarbazate Schiff base ligands using Cu K-edge X-ray absorption spectroscopy (XAS) and Kβ valence-to-core (VtC) X-ray emission spectroscopy (XES). By comparing the formally Cu(II) complexes [CuII(HL1)] (HL12− = dimethyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and [CuII(HL2)] (HL22− = dibenzyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and the formally Cu(III) complex [CuIII(L2)], distinct changes in transition energies are observed, primarily attributed to the metal oxidation state. Density functional theory (DFT) calculations demonstrate how an increased negative charge on the deprotonated L23− ligand stabilizes the Cu(III) center through enhanced charge donation, modulating the core transition energies. Overall, significant shifts to higher energies are noted upon metal oxidation, emphasizing the importance of scrutinizing ligand structure in XAS/VtC XES analysis. The data further support the redox-innocent role of the Schiff base ligands and underscore the criticality of ligand protonation levels in future spectroscopic studies, particularly for catalytic intermediates. The combined XAS-VtC XES methodology validates the Cu(III) oxidation state assignment while offering insights into ligand protonation effects on core-level spectroscopic transitions. [ABSTRACT FROM AUTHOR]

Density functional theory (DFT) was used to investigate the adsorption of twenty-four gases (SiH4, H2, Cl2, F2, CF4, CH4, CF2Cl2, N2, CHF3, OCS, N2O, AsH3, CH3Cl, COCl2, C2H2, C2H4, H2Se, H2S, PH3, COF2, CH3F, HCHO, (CH3)2O, and CH3NH2) on B12N12 and Al12N12 nanocages. Most of the studied gases are weakly (strongly) adsorbed on the B12N12 (Al12N12) nanocage. However, AsH3, H2Se, H2S, PH3, CH3F, HCHO, (CH3)2O, and CH3NH2 are strongly adsorbed on the B12N12 nanocage and H2, F2, CF4, CH4, and CF2Cl2 are weakly adsorbed on the Al12N12 nanocage. The most negative-valued molecular electrostatic potential (MESP) minimum (Vmin) corresponds to the electron-rich region (e.g., lone pair and π-bond) in the molecule. An important observation is that the adsorption energies of the gases on the B12N12 and Al12N12 nanocages are well correlated with the MESP Vmin values of the gases. Substantial changes are found in the DFT reactivity indices like chemical potential and hardness of the B12N12 and Al12N12 nanocages, mainly due to the strong gas adsorption. The quantum theory of atoms in molecules analysis suggests the covalent nature of interactions only in the AsH3/B12N12, H2Se/B12N12, H2S/B12N12, and PH3/B12N12 systems. [ABSTRACT FROM AUTHOR]

In this article, we present a meticulous computational study to foresee the effect of an oxygen-rich macrocycle on the reactivity for C–H activation. For this study, a widely studied nonheme Fe(IV)O molecule with a TMC (1,4,8,11-tetramethyl 1,4,8,11-tetraazacyclotetradecane) macrocycle that is equatorially attached to four nitrogen atoms (designated as N4) and acetonitrile as an axial ligand has been taken into account. For the goal of hetero-substitution, step-by-step replacement of the N4 framework with O atoms, i.e., N4, N3O1, N2O2, N1O3, and O4 systems, has been considered, and dihydroanthracene (DHA) has been used as the substrate. In order to neutralise the system and prevent the self-interaction error in DFT, triflate counterions have also been included in the calculations. The study of the energetics of these C–H bond activation reactions and the potential energy surfaces mapped therefore reveal that the initial hydrogen abstraction, which is the rate-determining step, follows the two-state reactivity (TSR) pattern, which means that the originally excited quintet state falls lower in the transition state and the product. The reaction follows the hydrogen atom transfer (HAT) mechanism, as indicated by the spin density studies. The results revealed a fascinating reactivity order, in which the reactivity increases with the enrichment of the oxygen atom in the equatorial position, namely the order follows N4 < N3O1 < N2O2 < N1O3 < O4. The impacts of oxygen substitution on quantum mechanical tunneling and the H/D kinetic isotope effect have also been investigated. When analysing the causes of this reactivity pattern, a number of variables have been identified, including the reactant-like transition structure, spin density distribution, distortion energy, and energies of the electron acceptor orbital, i.e., the energy of the LUMO (σ*z2), which validate the obtained outcome. Our results also show very good agreement with earlier combined experimental and theoretical studies considering TMC and TMCO-type complexes. The DFT predictions reported here will undoubtedly encourage experimental research in this biomimetic field, as they provide an alternative with higher reactivity in which heteroatoms can be substituted for the traditional nitrogen atom. [ABSTRACT FROM AUTHOR]

A novel, one-pot, three-component coupling (3-CCR) reaction of aromatic aldehydes, β-naphthol, and 6-amino-1,3-dimethyl uracil in a deep eutectic solvent (DES) has been developed as a highly efficient and selective method for the expedient synthesis of the densely functionalized 8,10-dimethyl-12-phenyl-8,12-dihydro-9H-benzo[5,6]chromeno[2,3-d]pyrimidine-9,11(10H)-dione framework in synthetically pleasing yield. The devised protocol adeptly harnesses the versatility of DESs, resulting in a straightforward, cost-effective, resilient, and environmentally sustainable synthetic approach. The resulting cascade adduct exhibits noteworthy antiproliferative activity against a variety of cancer cell lines, thereby showing promise as a potential anticancer drug candidate for breast and hepatocellular carcinoma with moderate to good IC50 values. The most potent compounds in the synthesized library, 4m and 4l, exhibit highly potent cytotoxicity against HepG2 and MCF7 cancer cell lines, with notable IC50 values of 46.39 and 28.21 μM, respectively. The present findings are corroborated by computational and molecular docking studies. The density functional theory (DFT) calculations underscore the pivotal role of the naphthyl ring in orchestrating the success of this intricate domino process in delivering the anticipated scaffolds in reasonable yields. [ABSTRACT FROM AUTHOR]

Potassium europium molybdate, KEu(MoO4)2, is an intriguing material known for its efficient luminescence properties attributed to Eu3+ ions and its polymorphic nature. Despite its significance, research on the metastable γ-phase has been limited, with no prior reports on its structure, particle morphology, and luminescence characteristics. In this study, both the stable α-phase and the metastable γ-phase of KEu(MoO4)2 were synthesized using solid-state and hydrothermal reaction methods, and their crystal structures, particle morphologies, and luminescence properties were comprehensively investigated. X-Ray diffraction analysis confirmed the formation of the triclinic α-phase and the orthorhombic γ-phase, with factor analysis results consistent with theoretically optimized structures, facilitating accurate structural determination. Both phases exhibited typical photoluminescence (PL) spectra of Eu3+ ions. However, in the γ-phase, the 5D0 → 7F2 transition appeared as a non-split peak with minimal Stark effect, attributed to differences in structural symmetry between the phases. A red-shift in the PL excitation edge was observed in the α-phase, which was attributed to a narrowed band gap resulting from the broadening of the O-p orbital in the valence band, as indicated by density functional theory (DFT) calculations. Additionally, KEu(MoO4)2 was doped with Y3+ ions to form K(Eu,Y)(MoO4)2, revealing a solid solubility limit of 40% in the α-phase, while the γ-phase displayed no solid solution limit. The estimated critical distance of Eu3+ ions suggested that Eu–Eu interactions contributing to concentration quenching are minimal in the stacking direction but significant in the in-plane direction, operating in the second shell. [ABSTRACT FROM AUTHOR]

A combined density functional theory (DFT) and microkinetic model (MKM) based approach is applied to design Pd-based A3B type bimetallic alloys – Pd3Cu, Pd3Ag and Pd3Au for hydrodechlorination (HDC) reaction of 4-chlorophenol (4-CP). The DFT results predict that the binding energy trend of 4-CP is Pd3Cu (111) [−257 kJ mol−1] > Pd (111) [−165 kJ mol−1] > Pd3Au (111) [−151 kJ mol−1] ≈ Pd3Ag (111) [−151 kJ mol−1]. The adsorbed 4-CP then undergoes C–Cl bond dissociation followed by hydrogenation to form phenol. Of all the surfaces, Pd3Ag (111) exhibits the least activation barrier for Cl dissociation from 4-CP (44 kJ mol−1), followed by Pd3Au (111) (66 kJ mol−1), Pd (111) (71 kJ mol−1) and Pd3Cu (111) (76 kJ mol−1) surfaces. The DFT generated data are utilized to construct an ab initio microkinetic model to calculate the turnover frequencies (TOFs) of 4-CP HDC. The Pd3Ag (111) surface displays the highest TOF, which could be attributed to the ease of Cl dissociation from the 4-CP molecule. However, the low TOF over the Pd3Cu (111) surface could be due to surface poisoning as a result of high 4-CP binding energy on the surface. For the C–Cl bond dissociation step, a positive degree of rate control is observed, which suggests that this step is crucial in ascertaining the HDC rate. [ABSTRACT FROM AUTHOR]

Because of their unique physicochemical integration mode, energetic host–guest solvates provide a balanced method to expand CL-20 high explosives. CL-20/hydrogen peroxide (H2O2) energetic solvates maintain their detonation performance by combining H2O2 molecules into a lattice akin to hydrate CL-20/H2O solvate (α-CL-20). Herein, using periodic density functional theory (DFT) calculation and molecular dynamics simulation, the structural evolution and intermolecular interaction mechanism of orthorhombic CL-20/H2O2 (o-CL-20/H2O2), monoclinic CL-20/H2O2 (m-CL-20/H2O2) and CL-20/H2O solvates were monitored by the vibrational spectrum and vibrational density of states (VDOS) in the THz region when the temperature was increased from 298 K to 558 K. There was greater similarity in the vibrational characteristics of THz spectra for o-CL-20/H2O2 and CL-20/H2O solvates that was supported by the thermal expansion anisotropy of lattice parameters and that of difference for the m-CL-20/H2O2 solvate. With increased temperature, spectral signals in the power spectrum of VDOS reflected the conformational evolution of CL-20 molecules in o-CL-20/H2O2 solvate and structural insensitivity of m-CL-20/H2O2 solvate. THz peaks of CL-20/H2O revealed the weakening of intermolecular interactions of CL-20 and H2O molecules, which were in agreement with the fact that H2O molecules more easily escape from host–guest solvates, whereas the H2O2 molecule was restricted in a cage of CL-20 molecules for the m-CL-20/H2O2 solvate. RDF and hydrogen bond (H-bond) interaction analyses were performed to further clarify stronger intermolecular H-bond interactions in the o-CL-20/H2O2 solvate as compared to that of the other two combined with H2O2 or H2O solvates. This finding introduces new insights into clarifying the formation mechanism of hydroxide with CL-20-based energetic host–guest solvates. [ABSTRACT FROM AUTHOR]

The frustrated Lewis pair (FLP) adducts PB{ECl2} (PB = iPr2P(C6H4)BCy2; Cy = cyclohexyl; E = Si, Ge) were used to access a bis(alkynyl)-functionalized silylene and a germylene; the goal behind preparing these species was to obtain new unsaturated main group polymers [E(C≡CSiMe3)2]n upon heating. While the silylene adduct PB{Si(C≡CSiMe3)2} was stable up to 150 °C, the heavier element congener PB{Ge(C≡CSiMe3)2} underwent a complicated rearrangement process accompanied by Cy-group migration and Ge(II)-alkyne coordination. Density functional theory computations were performed to understand the mechanistic pathway for the unusual rearrangement of PB{Ge(C≡CSiMe3)2}. [ABSTRACT FROM AUTHOR]

A series of charge transfer cocrystals with fluorescence properties involving 1,2,4,5-tetracyanobenzene (TCNB, C10H2N4) as acceptor, fluorene (FR, C13H10) and its bromide 2-bromofluorene (2-BrFR, C13H9Br), carbazole (CZ, C12H9N) and its bromide 2-bromocarbazole (2-BrCZ, C12H8BrN) as donor were synthesized via cocrystal design strategies. The formation mechanism of the crystal structure was explored by density functional theory at the molecular level. The stacking structure of the cocrystal was formed by the combination of charge transfer interactions, π–π interactions and hydrogen bonding. The N atom of donors in TCNB–CZ and TCNB–2-BrCZ could enhance the charge transfer, appearing as a red shift of the fluorescence emission wavelength. Conversely, the Br atom in TCNB–2-BrFR and TCNB–2-BrCZ weakens the charge transfer, giving a blue shift in the fluorescence emission spectrum. The four new cocrystals exhibit tunable luminescence from green (529 nm) to yellow (552 nm) and to red (604 nm and 614 nm). It was found that the introduction of N and Br atoms in the assembly units can not only regulate the luminescence range of the cocrystals, but also adjust the luminescence efficiency, which provides a strategy for the development of promising organic luminescent materials. [ABSTRACT FROM AUTHOR]

The structural and conductive properties of the synthetic tychite Na6Mg2(CO3)4SO4 (space group: Fd3¯) were explored. Optimal synthesis parameters were selected by varying the molar ratio of reagents, synthesis temperature and time. For structural descriptions, we carried out scanning electron microscopy, thermal analysis, and Raman and Fourier-transform infrared spectroscopy. We carried out theoretical and experimental studies of conductivity. Theoretical calculations were obtained using geometrical-topological analysis based on Voronoi partitioning (the evaluation of geometrical sizes of voids and channels), the bond valence site energy (BVSE) method (the fast calculation of migration energies, Em), kinetic Monte Carlo simulation (the estimation of ionic conductivity at different temperatures), and density functional theory (the precise assessment of Em and vacancy formation energies). The experimental techniques included electrochemical impedance spectroscopy EIS (total conductivity determination) and direct current DC polarization (electronic conductivity assessment) measurements. Na6Mg2(CO3)4SO4 was found to have a three-periodic Na+-ion migration map with an Em of 0.37 eV and 0.18 eV from BVSE and DFT results, respectively. The theoretical value of cationic conductivity was 2.6 × 10−7 S cm−1 at 100 °C. The experimental total conductivity was equal to 6.0 × 10−7 S cm−1 at 100 °C, which is close to theoretical results. Using additional DC polarization, the electronic contribution to the total conductivity was characterized as insignificant. [ABSTRACT FROM AUTHOR]

Metalloviologens, as emerging electron-transfer photochromic compounds, have shown intriguing properties such as radiochromism, photochromism and photoconductance. However, only a limited number of them have been reported so far. Exploration of new metalloviologens is strongly desired. Herein, we report a new solvothermally synthesized metalloviologen complex [CdCl2(ND)2]n (1, ND = 1,5-naphthalenes) that exhibits photochromic and intrinsic white light emission properties. Density functional theory calculation results reveal that the photochromism could be assigned to photoinduced electron transfer from chlorine atoms to ND molecules. The photoinduced charge-separated states are heat/air stable, attributed to the delocalization of ND and strong intermolecular π–π interactions. Besides, complex 1 consistently emits intrinsic white light when excited with 340–370 nm UV light, achieving high color rendering index (CRI) values (82.54–94.04). By adjusting the excitation wavelength, both "warm" and "cold" white light emission can be produced, making it suitable for the application of a white light emitting diode (WLED). Thus, this work demonstrates that the ND-based metalloviologen is not only helpful in producing photochromism, but also beneficial for creating white-light emission. [ABSTRACT FROM AUTHOR]

Lead-free inorganic perovskites have attracted intensive attention in the field of photodetectors owing to their high stability, non-toxicity, and remarkable photoelectric characteristics. Herein, we designed and developed a series of thus-far unreported lead-free all inorganic perovskite single crystals, K7Bi3X16 (X = Cl, Br). In particular, we resorted to cooling crystallization and intercalated K+ to inorganic Bi–Br and Bi–Cl frameworks as inorganic A-site cations, obtaining zero-dimensional (0D) K7Bi3X16 (X = Cl, Br) perovskite single crystals, which display suitable bandgaps, excellent electron mobility and low trap-state density, as analysed by experimental characterization and density functional theory (DFT) calculations. Accordingly, the vertical structure K7Bi3Br16 photodetector can achieve a fast ON/OFF switch under the irradiation of 395 nm light. When the light intensity is 5 mW cm−2 and the voltage is 3 V, the responsivity is calculated to be 0.052 mA W−1. The above characteristics make K7Bi3Br16 a promising material for fabricating ultraviolet photodetectors. [ABSTRACT FROM AUTHOR]

To overcome the limitations of the Fe(II)-activated percarbonate process for ACT removal, this study introduced cysteine as a complexing agent into the Fe(II)/SPC system and enhanced the degradation efficiency of ACT. Investigations were conducted on the effects of pH, temperature, common anions (Cl−, HCO3− and NO3−) in the water column, and humic acid (HA) on the degrading efficiency of the Cys/Fe(II)/SPC system. The results showed that under ideal conditions, 99.9% removal of ACT at 0.05 mM could be achieved. Alkaline environments inhibited ACT degradation, whereas acidic environments promoted it. Electron paramagnetic resonance (EPR) successfully detected ˙OH and O2˙−, but no 1O2 radical signal was detected. Further research was carried out to determine how much ˙OH and O2˙− contributed to the oxidation process. The results showed that both ˙OH and O2˙− contributed to the degradation of the ACT, with ˙OH's contribution being particularly significant. Mass spectrometry analysis was used to determine the structure of the oxidation products. Vulnerable sites in ACT were predicted using density functional theory. Using LC-MS/MS analysis, seven intermediates of the Cys/Fe(II)/SPC degradation of ACT were individually identified. The results showed that the acetylamino group on ACT and the C–N bond on the benzene ring are susceptible to attack by ˙OH. The T.E.S.T. toxicity prediction model was used to predict the toxicity of ACT and its intermediates. The results showed a trend towards reduced acute toxicity and overall developmental toxicity. [ABSTRACT FROM AUTHOR]

The global market of fossil carbon-derived adipic acid (AA) was over 3 million tons in 2022, emitting 3.1 million tons of the potent greenhouse gas N2O. Alternative biomass-derived feedstocks offer a sustainable option to replace fossil carbon, but alternative pathways for AA synthesis are also required to curb the substantial emissions associated with the process. A novel and sustainable approach to synthesize AA is by coupling biomanufacturing and electrocatalysis. Biologically-produced cis,cis-muconic acid (ccMA) from sugars and lignin monomers has recently gained significant attention as a precursor to AA, as it can be electrochemically hydrogenated to AA using water-derived (instead of fossil-derived) hydrogen and electricity generated from wind energy. For the first time in literature, we demonstrate appreciable electrochemical production of AA using supported palladium nanoparticles. The performance of this system contrasts with that of palladium foil or platinum-based catalysts, which produced little AA. Density functional theory calculations on model surfaces of palladium and platinum suggest that the reduction of ccMA to trans-3-hexenedioic acid occurs through an outer sphere proton-coupled electron transfer mechanism, while subsequent reduction to AA preferentially occurs on surface terrace sites. Our calculations also explain the exceptional performance of palladium nanoparticles compared to palladium- and platinum-based foils, attributing the more favorable activation energy barriers found on palladium terraces to the relatively moderate binding strength of adsorbed species. These results suggest structure-sensitive catalyst design strategies that maximize the exposure of terrace atoms for further improvement of the ccMA electrochemical hydrogenation process. [ABSTRACT FROM AUTHOR]

Density functional theory plus Hubbard U (DFT+U) methodology was used to calculate the structures and energetic landscapes of CeSiO4, including its stetindite and scheelite phases from ambient pressure to ~24 GPa. To ensure accurate simulations of the high-pressure structures, assessments of strain-stress methods and stress-strain methods were conducted in prior, with the former found to have a better agreement with the experimental result. From DFT calculations the equation of states (EOS) of both stetindite and scheelite were further obtained, with the fitted bulk moduli being 182(2) GPa and 190.0(12) GPa, respectively. These results were found to be consistent with the experimental values of 177(5) GPa and 222(40) GPa. Furthermore, the calculated energetics suggest that the stetindite structure is more thermodynamically stable than the scheelite structure at a pressure lower than 8.35 GPa. However, the stetindite → scheelite phase transition was observed experimentally at a much higher pressure of ~15 GPa. A further phonon spectra investigation by the density functional perturbation theory (DFPT) indicated the Eg¹ mode is being softened with pressure and becomes imaginary after 12 GPa, which is a sign of the lattice instability. Consequently, it was concluded that the stetindite → scheelite transition is predominantly initiated by the lattice instability under high-pressure. [ABSTRACT FROM AUTHOR]

The quantitative structure-property relationship (QSPR) of constrained geometry catalysts (CGCs) has been analyzed by combining density functional theory (DFT) and multivariate linear regression (MLR). QSPR models for determining the reaction energy barriers of ethylene and 1-octene and molecular descriptors were established and validated with a testing set. At the initiation stage, the quaternary QSPR models for ethylene and 1-octene feature R² values of 0.90 and 0.82, respectively, while the corresponding leave-one-out Q² values for ethylene and 1-octene are determined to be 0.82 and 0.69. Using the generated QSPR models, the electronic effect was proven to be more critical for determining the energy barriers of ethylene and 1-octene insertion processes. At the propagation stage, the quaternary QSPR models for ethylene and 1-octene feature R² values of 0.97 and 0.96, respectively, while the corresponding leave-one-out Q² values for ethylene and 1-octene are determined to be 0.93. Particularly, the impact of the steric effect on the energy barriers of ethylene and 1-octene insertion is more pronounced. Furthermore, the correlation between the corresponding energy barriers and experimental activities with three series of CGCs was discussed, which revealed that theoretical calculations are consistent with the experimental results. [ABSTRACT FROM AUTHOR]

A metal-free one-pot cascade process involving reduction of nitroarenes, cyclization, and sequential hydrogenation of imines with B2cat2 and water was developed to construct dihydroquinoxalinones and tetrahydroquinoxalines directly from readily available 2-nitroanilines or o-dinitrobenzenes with α-ketoesters and a-diketones. This strategy provides various dihydroquinoxalinones and tetrahydroquinoxalines in good to excellent yields and tolerance to many functional groups. Mechanism studies by control experiments and density functional theory (DFT) calculations show that this cascade procedure involves the deoxygenative reduction of nitroarenes, the Maillard reaction, and hydrogenation to produce dihydroquinoxalinones and tetrahydroquinoxalines. This method aims to reduce the environmental impact while maintaining high yields and selectivity for both nitroarene reduction and the synthesis of dihydroquinoxalinones and tetrahydroquinoxalines. [ABSTRACT FROM AUTHOR]

Catalytic function in organometallic complexes is achieved by carefully selecting their central metals and ligands. In this study, the effects of a metal and a ligand on the kinetics and thermodynamics of hydrogen activation, hydricity degree of the hydride complex, and susceptibility to electronic oxidation in bioinspired NiFe complexes, [NiIIX FeII(Cl)(CO)Y]+ ([NiFe(Cl)(CO)]+; X = N,N′-diethyl-3,7-diazanonane-1,9-dithiolato and Y = 1,2-bis(diphenylphosphino)ethane), were investigated. The density functional theory calculations revealed that the following order thermodynamically favored hydrogen activation: [NiFe(CO)]2+ > [NiRu(CO)]2+ > [NiFe(CNMe)]2+ ∼ [PdRu(CO)]2+ ∼ [PdFe(CO)]2+ ≫; [NiFe(NCS)]+. Moreover, the reverse order thermodynamically favored the hydricity degree. [ABSTRACT FROM AUTHOR]

In this work, density-functional theory (DFT) was used to investigate the geometry and electronic structure of Run(n = 1–6,10) supported on CeO2(110) (Run(n = 1–6,10)/CeO2(110)) and their electrocatalytic properties for the N2 reduction reaction (NRR). The results indicated that there is a strong metal–support interaction between Run and CeO2(110), which leads to large surface distortion and stabilized Run. On Run(n = 1–6,10)/CeO2(110), N2 captured in the end-on mode is thermodynamically more favorable than that captured in the side-on mode; however, the side-on mode can lead to stronger activation of N2 which promotes the following protonation step of N2. For Run(n = 3,5,6)/CeO2(110), the electrochemical NRR prefers to occur via an enzymatic mechanism with limiting potentials of −0.31, −0.53 and −0.66 V. The electrocatalytic activity of Run(n = 1–6,10)/CeO2(110) for the NRR shows a strong size dependence. For Ru3/CeO2(110), it has the lowest absolute value of limiting potential, and with the increase in n (n > 3), the limiting potential becomes more negative. Moreover, Ru3/CeO2(110) shows high selectivity and stability. This study gives valuable insights for designing effective catalysts for the NRR. [ABSTRACT FROM AUTHOR]

Non-acidic hydrogen evolution systems have a low concentration of hydrogen ions, and the H2 evolution reaction (HER) is often limited by the water dissociation step. Preparing catalysts that can accelerate water dissociation is a common method for achieving high-efficiency evolution of hydrogen. In the current work, the performance of a hydrogen evolution system was first improved by introducing CO2 to transform the presence status of H2O. According to density functional theory (DFT) calculations, water reacts with CO2 to produce carbonic acid which can reduce the barrier of adsorbed H generation. Subsequently, under same pH conditions, a constructed dye-sensitized Ni–CO2 system shows an H2 evolution rate 1.5 times higher than that shown by dye-sensitized Ni. This result indicates that transforming the presence status of H2O may be a new strategy for further improving H2 evolution efficiency. [ABSTRACT FROM AUTHOR]

Mastery with regard to the evolution of the chemical form of fission products in the primary circuit is essential for the development and improvement of models, which can predict the release of fission products into the primary loop under normal or accidental operating conditions and analyze the consequences of severe accidents. Here, the chemical forms of fission products in the primary loop of the HTR-PM are predicted by the thermodynamic database method. Furthermore, the microscopic mechanisms of the reactions between radionuclides Cs and I with steam are systematically investigated using density functional theory. The predominant reaction products of Cs + H2O and I + H2O include CsO, CsOH, IO, IOH, and HI. The bond evolution properties are analyzed using the electron localization function, quantum theory of atoms in molecules, bond order density, and mayer bond order. The reaction rate constants are determined utilizing the variational transition state theory. Within the temperature range of the HTR-PM primary circuit (250–750 °C), the reaction rate constant of OIH2 is effectively zero, and the reaction rate constant of HI is higher than that of IOH. The results of the above microscopic calculations are consistent with the macroscopic thermodynamic calculations, and these data serve as valuable ESI for the experiments. [ABSTRACT FROM AUTHOR]

Inhibition of intraerythrocytic iron uptake by plasmodium parasites is a viable alternative antimalarial mode of action to that adopted by artemisinins, since microorganisms require iron for growth and replication, but this has received less research attention. Against this backdrop, an in silico study on bis-thiosemicarbazones (TSCs) with significant antiplasmodial properties as Fe(III)-selective chelators and inhibitors of hemozoin formation is undertaken herein using density functional theory (DFT), molecular docking and molecular dynamics (MD) simulations. From the large contrasts in calculated binding energies for Fe(III) and Fe(II) sequestration in aqueous solution at DSD-BLYP/def2-TZVPD level of theory (−1162.99 to −1187.64 kcal mol−1 and −671.75 to −687.60 kcal mol−1, respectively), the TSCs are potential Fe(III)-selective chelators as desired for chelation therapy. Based on their satisfactory oral bioavailability profiles, the TSCs are found to be adequately drug-like. They are therefore expected to easily penetrate parasitized erythrocytes and inhibit the growth/development of plasmodium parasites by scavenging and externalizing intraerythrocytic ferric iron. Moreover, docking and adsorption studies of these TSCs onto the (001) face of the β-hematin crystal have yielded favorable binding free energies (−9.874 to −11.83 kcal mol−1) and negative adsorption energies (−84.61 to −109.80 kcal mol−1), respectively. The adsorption energies obtained herein are either comparable or more negative than those obtained in previous studies for well-known antimalarial drugs. Therefore, besides Fe(III)–chelation, the antiplasmodial activities of the TSCs studied are also attributable to inhibition of β-hematin/hemozoin formation, which has a cascade effect on plasmodium parasite survival. From our findings, in vitro β-hematin inhibition assays on these TSCs are recommended. [ABSTRACT FROM AUTHOR]

The electrochemical selective oxidative transformation of lignin feedstocks into valuable oxygenated aromatics is essential to establish a sustainable biorefinery. In this study, we used a rhombohedral ZnIn2S4 (R-ZIS) electrocatalyst to realise the efficient anodic cleavage of C-O bonds in benzyl phenyl ether (BPE), an a-O-4 lignin model compound, to a series of industrially relevant oxygenated mono-aromatics. The reaction occurred at +2 VAg/AgCl, 65 °C, and atmospheric pressure. In optimised conditions, the reaction achieved over 99% conversion rate with a Faraday efficiency of 51.6% at 91.3% conversion of BPE, that is greater than most known electrocatalytic oxidative cleavage examples. The ZnIn2S4 electrocatalyst was deposited on a carbon cloth support, and its structural properties and surface morphology were extensively investigated. Systematic potential controlled electrolysis coupled with 18O isotopic labelling confirmed that C-O scission occurred exclusively between the benzylic carbon and phenolic oxygen. Furthermore, substrate competition studies were conducted to compare the electrocatalytic performance of the R-ZIS catalyst with that of its structural analogue, hexagonal ZnIn2S4, in terms of BPE and monoaromatics conversion. The experimental results were supported by density functional theory calculations. The substrate scoping study revealed the suitability of the R-ZIS induced electrocatalytic system for a variety of substituted a-O-4/ß-O-4 model dimers. Overall, this work demonstrates an efficient anodic process that can enable the atom-efficient valorisation of lignin to produce oxygenated aromatics. The proposed approach can complement the numerous existing reductive lignin cleavage methods. [ABSTRACT FROM AUTHOR]

Halogenated nitroarenes' hydrogenation on metal-based catalysts without dehalogenation to synthesize halogenated amines is a research challenge. Herein, using a covalent organic framework (COF) as a support and benefiting from strong metal-support interactions (SMSIs), ultrafine Pt nanoparticles were successfully anchored on a polyimide-based covalent triazine framework, to construct an electron-rich Pt active site-based catalyst (Pt/TAPT-COF). The electronic regulation from the COF contributed to both the selective hydrogenation of halogenated nitrobenzenes and the tandem hydrogenation-coupling reaction of halogenated nitrobenzenes with aldehyde compounds to synthesize halogenated amines with high selectivity under mild reaction conditions. According to density functional theory calculations, the hydrogenation of halogenated nitrobenzene is exothermic with strengthened absorption, confirming the existence of SMSIs to explain the high activity of Pt/TAPT-COF in hydrogenation reactions. Thus, this work provides a facile strategy to fabricate an electron-rich Pt-based catalyst enabled by SMSIs to selectively catalyze the synthesis of halogenated anilines and halogenated secondary amines. [ABSTRACT FROM AUTHOR]

The development of highly efficient and environment friendly methods for arsenic pollution treatment has attracted special attention. Herein, a new polyoxometalate-thiacalix[4]arene-based metal-organic complex [Ag2L(HL)][PW12O40]·2C2H5OH·2CH3CN (1) (L = thiacalix[4]arene-based ligand) was synthesized and applied for BiVO4 (BVO) surface modification to efficiently enhance the simulated sunlight-driven photoelectrocatalytic oxidation of arsenic(III). Compared with the pristine BVO, the removal efficiency of arsenic(III) was drastically increased to 312% at 0.6 V with the optimized 1@BVO photoanode (B1-20) versus the saturated calomel electrode (SCE) under the simulated sunlight (100 mW cm-2). The removal efficiency of arsenic(III) (25 mg L-1) with B1-20 was up to 100% within 40 min with a faradaic efficiency of 45%. More importantly, electron spin resonance measurements and reactive species trapping experiments demonstrated that the Z-scheme heterojunction formation of 1 plays a key role in the enhanced photoelectrocatalytic performance of 1@BVO. Furthermore, density functional theory (DFT) calculations were used to investigate the relationship between the photoelectrocatalytic properties and the structure of 1. This work developed a new photoelectrocatalytic application for the polyoxometalate-thiacalix[4]arenebased metal-organic complexes by their efficient combination with BVO. [ABSTRACT FROM AUTHOR]

Inspired by the reference R with the IUPAC name ((Z)-2-(aminomethyl)-3-(5-((3-methyl-5-(7-(4-methyl-5-(5,10,15-trimethyl-10,15-dihydro-5H-diindolo[3,2-a:3′,2′-c]carbazol-3-yl)thiophen-2-yl)benzo[c][1,2,5]thiadiazol-4-yl)thiophen-2-yl)ethynyl)furan-2-yl)acrylic acid)), six new organic (D–π–A) dyes for dye-sensitized solar cell (DSSC) applications have been designed. The designed molecules have an electron donor (D), triazatruxene, connected through different π-bridges and an electron acceptor (A), 2-cyanoacrylic acid. The key parameters of the optoelectronic and photoelectric performances were computed by density functional theory (DFT) and time-dependent density functional theory (TD-DFT). Compared to the original dye R, the designed compounds have a higher light harvesting ability with an absorption spectrum that appeared around the infrared region. The maximum absorption wavelength shifted to red from 78 nm to 148 nm, and the light-harvesting efficiency (LHE) curve broadened in the visible region and excellent electron injection efficiency was observed. All these contribute to better short-circuit current density (JSC) and power conversion efficiency (PCE). The results obtained through the global evaluation model for the reference dye R were JSC = 19.21 mA cm−2, VOC = 0.838 V, and PCE = 13.92%. These values are closer to the experimental results (JSC = 19.74 mA cm−2, VOC = 0.957 V, and PCE = 13.4%). The Tat-2 dye achieved a PCE of 23.75%. Therefore, it can be considered a candidate dye for high-yield DSSCs. [ABSTRACT FROM AUTHOR]

A new (La,Sr)(Al,Ta)O3 (LSAT) crystal is focused on in this paper to be used as an ideal substrate for preparing perfect BiFeO3 thin films. The crystal structures are designed with a low lattice mismatch between LSAT and BiFeO3. LSAT crystals were grown by the Czochralski method. In order to get colourless crystals with high transmittance, density functional theory is used to simulate the crystals with different defects. From the results, it is found that the colour centre originates from the defect of VSr + VO or VSr + 2VO. Thus, it is necessary for the crystals to be annealed in O2 and then in N2. High-quality BiFeO3/LSAT thin films will have promising application prospects. [ABSTRACT FROM AUTHOR]

In this paper, we synthesized layered crystals of bis(μ2-chlor)-tris(triphenylphosphine)-di-copper(I) (CTC) and bis(μ2-bromo)-tris(triphenylphosphine)-di-copper(I) (BTC) via electrochemical synthesis in an ambient environment. The crystal stands edge-on to the copper substrate in the electrochemical synthesis, which would enhance the charge transfer between the crystal and the substrate, promoting its photoelectric properties. Combined with density functional theory calculations, the optical absorption and emission are the crystals were studied to obtain a clarified mechanism. Using a chemical etching strategy, we can obtain BTC microtubes with tunable cavities, which can be used as microscopic containers. [ABSTRACT FROM AUTHOR]

Herein, nanocomposites made of Ni nanoparticles in situ distributed in an amorphous silicon nitride (Ni/a-Si3N4) matrix, on the one hand, and within an amorphous silicon dioxide (Ni/a-SiO2) matrix, on the other hand, were synthesized from the same Ni-modified polysilazane precursor. In both compounds, the Ni/Si atomic ratio (0.06–0.07), average Ni nanocrystallite size (7.0–7.6 nm) and micro/mesoporosity of the matrix were rigorously fixed. Hydrogen (H2)-temperature-programmed desorption (TPD) profile analysis revealed that the activation energy for H2 desorption at about 100–130 °C evaluated for the Ni/a-Si3N4 sample (47.4 kJ mol−1) was lower than that for the Ni/a-SiO2 sample (68.0 kJ mol−1). Mechanistic study with X-ray photoelectron spectroscopy (XPS) analysis and density functional theory (DFT) calculations revealed that, at Ni nanoparticle/matrix heterointerfaces, Ni becomes more covalently bonded to N atoms in the a-Si3N4 matrix compared to O atoms in the a-SiO2 matrix. Therefore, based on experimental and theoretical studies, we elucidated that nickel–nitrogen (Ni–N) interactions at the heterointerface lead to remarkable Ni d band broadening and downshifting of the d band center relative to those generated by Ni–oxygen (Ni–O) interactions at the heterointerface. This facilitates H2 desorption, as experimentally observed in the Ni/a-Si3N4 sample. [ABSTRACT FROM AUTHOR]

A novel triple helical-like complex [Dy2K2L3(NO3)2]·3DMF (1) based on a designed Schiff base N′1,N′3-bis((E)-3-ethoxy-2-hydroxybenzylidene)-malonohydrazide (H4L) was synthesized with good chemical and thermal stabilities. Single-crystal X-ray structural analysis showed that 1 presents a tetranuclear triple helical-like structure via the coordination mode of Dy : K : L with 2 : 2 : 3 stoichiometry. Fluorescence measurements showed that 1@EtOH has excellent fluorescence turn-on/off response ability for aluminium ions and 4,5-dimethyl-2-nitroaniline (DMNA) with outstanding selectivity, sensitivity, and anti-interference ability. The calculated limit of detection (LOD) values for 1@EtOH to Al3+ and DMNA were found to be 0.53 and 3.33 μM, respectively. Density functional theory (DFT) calculation showed that the fluorescence response mechanism can be explained by the photoinduced electron transfer (PET) mechanism; meanwhile, the inner filter effect (IFE) of DMNA can also affect the emission of 1@EtOH. [ABSTRACT FROM AUTHOR]

Porphyrins have been widely used in designing photocatalyst systems. However, finding an effective strategy to improve the intrinsic photocatalytic activity of porphyrin molecules remains a challenge. Here, two new porphyrins, meso-tetra(5-carboxyfuryl)porphyrin (H2TCFP) and meso-tetra(5-carboxythienyl)porphyrin (H2TCTP), were successfully synthesized and compared with meso-tetra(m-carboxyphenyl)porphyrin (H2TmCPP), to clarify the influence of the organic unit bridging the carboxyl acid group with the porphine ring on the photocatalytic activity of porphyrin for H2 evolution from water splitting. The H2 evolution rates of 10.8 mmol g−1 h−1 observed for H2TCFP and 9.7 mmol g−1 h−1 for H2TCTP are both larger than 8.0 mmol g−1 h−1 observed for H2TmCTP under optimal conditions. The best photocatalytic activity observed for H2TCFP was investigated through experiments and density functional theory (DFT) calculations and was interpreted in terms of the combined effect of several key factors of the entire photocatalytic process, including the high absorptivity of UV light, high separation efficiency of photogenerated carriers, and low Gibbs energy required for associated water splitting. Meanwhile, the concentration-dependent performance of photocatalytic activity was analyzed and attributed to the aggregation and light-bleaching effect exerted on porphyrins. [ABSTRACT FROM AUTHOR]

MoSe2 as one graphene-like 2D transition metal selenide has attracted great attention. However, its application for the hydrogen evolution reaction (HER) is still restricted by the poor electrical conductivity and structural restacking. In this work, an excellent electrocatalyst for hydrogen production is developed based on the in situ synthesis of V-doped MoSe2 confined on carbon black nanoparticles (denoted as V-MoSe2/CB) via a sol–gel process. The characterization results show that the carbon black nanoparticles can protect the V-MoSe2 nanosheets from agglomeration, resulting in ultra-thin thickness and short vertical lattice arrays. Meanwhile, density functional theory (DFT) calculations indicate that vanadium doping can optimize the electronic structure of MoSe2. Accordingly, compared to the pure MoSe2, V-MoSe2 and MoSe2/CB electrocatalysts, V-MoSe2/CB exhibits improved electrocatalytic activity with a small overpotential of 166 mV at −10 mA cm−2 and a small Tafel slope of 65 mV dec−1. This work paves a new way for improving the HER performance through synergistic morphology, structure and electronic regulation. [ABSTRACT FROM AUTHOR]

Encouraged by the promising performance of C60-graphene single-molecule transistors observed in experiments, two types of Fen/C60-GNR (n = 2 and 4 and GNR = graphene nanoribbon) molecules with Fe atoms sandwiched between the upper and lower GNR layers were designed and their electronic and transport properties were investigated by employing density functional theory (DFT) and nonequilibrium Green's function (NEGF) methods. Adding the Fe atoms induces high spin magnetism in the systems. Within the considered bias, almost all Fe2/C60-GNR devices generate double NDR peaks, and some of the Fen/C60-GNR devices (n = 2 and 4) possess a large peak-to-valley current ratio R = Ipeak/Ivalley (>400), implying potential applications in developing on–off–on/off–on–off current switches. The NDR character originates from the crossing of the frontier molecular orbitals. In addition, these systems show distinct spin-polarized transport characteristics, with up-spin channels displaying higher conductivity than down-spin pathways. The spin filter efficiency (SFE) oscillates up and down as bias is scanned for almost all devices, suggesting the possibility of designing on–off–on/off–on–off current switches as well as up–down spin switches. All these findings provide guidance for exploring single molecular devices with promising properties combined with graphene, fullerenes, and transition metals. [ABSTRACT FROM AUTHOR]

This work explores the characteristics of two-dimensional (2D) titanium carbide (Ti3C2 MXene) and utilizes first-principles study to weigh its potential for supercapacitor applications. Scanning electron microscopy images confirm the layered morphology of the MXene, and energy-dispersive X-ray spectroscopy (EDX) analysis supports the extraction of aluminum from the MAX phase. Fourier-transform infrared (FTIR) spectroscopy confirms the presence of oxygen-based functional groups on the surface of the MXene and X-ray diffraction (XRD) patterns validate its hexagonal crystalline structure. Cyclic voltammetry (CV) analysis reveals the presence of redox peaks, indicating the pseudocapacitive behaviour of the fabricated electrode. Additionally, galvanostatic charge–discharge (GCD) measurements yield a calculated specific capacitance of 370 F g−1. Electrochemical impedance spectroscopy (EIS) substantiates the low impedance resulting from the layered structure via the adequate adsorption/desorption of cations. The utilization of first-principles density functional theory (DFT) calculations reveals the merging of conduction and valence bands, signifying effective conductivity. Both the total and partial density of states cross the Fermi level, indicating a highly efficient charge mobility process. The combination of prominent surface redox reactions and excellent conductivity contributes to the superior specific capacitance of the fabricated electrode. Overall, these results highlight the excellent electrochemical properties of the Ti3C2 MXene electrode, declaring it as a promising candidate for supercapacitor applications. [ABSTRACT FROM AUTHOR]

Hydrogen peroxide (H2O2) electrosynthesis via the two-electron oxygen reduction reaction (2e− ORR) represents a green alternative to the energy-intensive anthraquinone process. However, the practical application of this method is limited by the lack of cost-effective and high-performance electrocatalysts. Reported here is a hybrid catalyst composed of nickel (Ni) clusters immobilized onto the surface of two-dimensional siloxene nanosheets (Ni/siloxene), which exhibits excellent efficiency and selectivity in electrocatalytic oxygen reduction to H2O2 in an alkaline medium, demonstrating a standard 2e− pathway with >95% H2O2 selectivity across a wide potential range. Experimental results disclose that the high performance of Ni/siloxene can be traced to a synergy of the Ni clusters and the oxygen-rich surface of siloxene. Density functional theory (DFT) calculations further reveal a weakened interaction between Ni/siloxene and *OOH and the consequently reduced energy barrier for the *OOH protonation toward H2O2 desorption, thus leading to a high 2e− ORR reactivity and selectivity. This work provides a valuable and practical guidance for designing high-performance 2e− ORR electrocatalysts based on the rational engineering of the metal–support interaction. [ABSTRACT FROM AUTHOR]

The electrochemical reduction of CO2 to HCOOH is considered one of the most appealing routes to alleviate the energy crisis and close the anthropogenic CO2 cycle. However, it remains challenging to develop electrocatalysts with high activity and selectivity towards HCOOH in a wide potential window. In this regard, Ag/Bi2O2CO3 was prepared by an in situ electrochemical transformation from Ag/Bi2O3. The Ag/Bi2O2CO3 catalyst achieves a faradaic efficiency (FE) of over 90% for HCOOH in a wide potential window between −0.8 V and −1.3 V versus the reversible hydrogen electrode (RHE). Moreover, a maximum FE of 95.8% and a current density of 15.3 mA cm−2 were achieved at a low applied potential of −1.1 V. Density functional theory (DFT) calculations prove that the high catalytic activity of Ag/Bi2O2CO3 is ascribed to the fact that Ag can regulate the electronic structure of Bi, thus facilitating the adsorption of *OCHO and hindering the adsorption of *COOH. This work expands the in situ electrochemical derivatization strategy for the preparation of electrocatalysts. [ABSTRACT FROM AUTHOR]

An enlarged version of the ubiquitous tetrathiafulvalene-tetrabenzoic acid is described, with 4,4′-biphenyl moieties as spacers between the coordination moieties and the electroactive core. The obtained rectangular ligand has a 14 × 22 Å2 size and is combined with Zn(II) under solvothermal conditions to yield a coordination polymer endowed with large cavities of ca. 15 × 11 Å2/10 × 10 Å2. The topology of the material is discussed in detail using the Points of Extension and Metals (PE&M) or the Straight-rod (STR) representation, and the sqc1121 or tfo topological type of the structure is observed, respectively. Its stability towards solvent removal and electrical properties are discussed. The material does not present any permanent porosity upon desolvation according to nitrogen sorption measurements at 77 K. Nevertheless, a significant increase in conductivity is observed on compressed pellets of the material upon post-synthetic oxidation with iodine. Raman spectroscopy combined with density functional theory (DFT) calculations has been used to characterize the oxidation state of tetrakis(4-carboxylic acid biphenyl)tetrathiafulvalene for coordination polymers. [ABSTRACT FROM AUTHOR]

In this work, the interfacial self-assembly behavior of [1,1′:3′,1′′-terphenyl]-4,4′′-dicarboxylic acid (TDA) and the regulation of the introduced guest molecules (trimesic acid (TMA) and coronene (COR)) on TDA's mono-component system were investigated by scanning tunneling microscopy (STM), and the formation mechanism was investigated by density functional theory (DFT). Newly added TMA molecules destroyed the single-row structure formed by TDA self-assembly and formed a new hexagonal co-assembly structure with TDA molecules. When COR was introduced into this system, the co-assembly structure collapsed and the resulting structure was dependent on the concentration of the COR solution. [ABSTRACT FROM AUTHOR]

With the current food demand, pesticides have become some of the most important compounds to maintain food quality; however, this requires the development of methodologies that allow fast, sensitive, and low-cost screening for these contaminants. Surface-enhanced Raman spectroscopy is an emerging solution since the interaction between the analyte and metallic nanostructures increases the Raman signals, enabling trace detection and a chemical-specific measurement. In this way, the fast detection of contaminants is possible, and further advances may enable portable assays. In this work, SERS substrates with silver nanosheets (AgNSs) on a copper surface were synthesized, producing a strong SERS effect and a reproducible signal intensity from methylene blue probe molecules at an optimal reaction time of 1 min. A quantitative analysis of the pesticide imidacloprid was then performed by applying a PLSR chemometric model, revealing a high linear correlation between the reference values and the predicted values of the pesticide (Rcv2 = 0.9732 and RMSECV = 0.1239). AgNS substrates were used to determine the feasibility of using this methodology for screening imidacloprid in real bee honey samples obtained through QuEChERS extraction, and an average recovery of 75.5% ± 0.08 was obtained. In addition, density functional theory simulations were carried out to elucidate the possible molecular interaction with the SERS surface and to assign the observed vibrational modes of imidacloprid. SERS is thus demonstrated to be an alternative to conventional pesticide detection techniques. [ABSTRACT FROM AUTHOR]

The design of low-cost and high-performance bifunctional catalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) is of great significance for overall water splitting. Herein, RuNi single atom alloy (SAA) decorated on reduced graphene oxide (RuNi@rGO) was synthesized by a facile strategy for use as a bifunctional HER/OER catalyst. The as-obtained RuNi@rGO catalyst exhibits outstanding electrocatalytic activities with an ultralow overpotential for the HER (15 mV) and the OER (240 mV) at a current density of 10 mA cm−2. Density functional theory (DFT) calculations demonstrate that the introduction of Ru single atoms can evidently change the electron distribution and coordination environment around Ni, and reduce the intermediate's adsorption free energy of RuNi@rGO, thus facilitating the HER/OER catalytic rate. Moreover, when used as the cathode and anode of a two-electrode system, the RuNi@rGO-based water splitting device exhibits a low potential of 1.52 V at a current density of 10 mA cm−2, as well as a high faradaic efficiency almost up to 100%, making RuNi@rGO bifunctional electrocatalysts attractive for energy storage and conversion. [ABSTRACT FROM AUTHOR]

Herein, we report the synthesis and photoluminescence properties of a new 1,3-dioxo-2-(1H-tetrazol-5-yl)-2,3-dihydro-1H-benzo[de]isoquinoline-6,7-dicarboxylic (H3L) ligand and three coordination polymers (CPs). Compound [Zn(ntca)DMF]n·DMF (1) (ntca2− = 1,4,5,8-naphthalenetetracarboxylate 1,8-monoanhydride, DMF = N,N-dimethylformamide) formed 1D coordination polymer chains packed by hydrogen bonding interactions. On its part, compounds namely [(CH3)2NH2](Zn2(μ-OH)(L)(5-NH2-tetrazolate)n·2H2O (2) and [(CH3)2NH2](ZnL)n (3) (where H3L stands for 1,3-dioxo-2-(1H-tetrazol-5-yl)-2,3-dihydro-1H-benzo[de]isoquinoline-6,7-dicarboxylic acid) crystallize as 2D-layered and 3D anionic frameworks containing dimethylammonium cations occupying the voids. Photoluminescence (PL) measurements have been performed in the solid state on all CPs and ligands to characterize their emission properties, including variable-temperature spectra, lifetime and efficiency. Moreover, the photophysical properties have been studied from the theoretical viewpoint by means of time dependent density functional theory (TD-DFT) in order to elucidate the mechanisms and electronic transitions governing the process. Compounds 1 and 3 present an intense blue luminescence which was originated in the electronic transitions of the ntca2− and the L3− ligands. Compound 2 displays a lower quantum yield which could be tentatively attributed to the weak π–π interactions of the aromatic clouds of L3− or the molecular vibrations and/or possible rotational motions of the 5-amino-tetrazolate co-ligand. [ABSTRACT FROM AUTHOR]

This study describes the discovery of a unique ionic cocrystal of the active pharmaceutical ingredient (API) ponatinib hydrochloride (pon·HCl), and characterization using single-crystal X-ray diffraction (SCXRD) and solid-state NMR (SSNMR) spectroscopy. Pon·HCl is a multicomponent crystal that features an unusual stoichiometry, with an asymmetric unit containing both monocations and dications of the ponatinib molecule, three water molecules, and three chloride ions. Structural features include (i) a charged imidazopyridazine moiety that forms a hydrogen bond between the ponatinib monocations and dications and (ii) a chloride ion that does not feature hydrogen bonds involving any organic moiety, instead being situated in a "square" arrangement with three water molecules. Multinuclear SSNMR, featuring high and ultra-high fields up to 35.2 T, provides the groundwork for structural interpretation of complex multicomponent crystals in the absence of diffraction data. A 13C CP/MAS spectrum confirms the presence of two crystallographically distinct ponatinib molecules, whereas 1D 1H and 2D 1H–1H DQ–SQ spectra identify and assign the unusually deshielded imidazopyridazine proton. 1D 35Cl spectra obtained at multiple fields confirm the presence of three distinct chloride ions, with density functional theory calculations providing key relationships between the SSNMR spectra and H⋯Cl− hydrogen bonding arrangements. A 2D 35Cl → 1H D-RINEPT spectrum confirms the spatial proximities between the chloride ions, water molecules, and amine moieties. This all suggests future application of multinuclear SSNMR at high and ultra-high fields to the study of complex API solid forms for which SCXRD data are unavailable, with potential application to heterogeneous mixtures or amorphous solid dispersions. [ABSTRACT FROM AUTHOR]

The extraction of lead-212 (212Pb) from radioactive thorium (Th) waste is immensely important, as it serves to mitigate environmental risks associated with radioactive waste and provides a vital source for medical isotopes. To economically extract 212Pb from thorium, we synthesized a novel extractant known as 2,13-disulfonyldiethylamine dibenzo-18-crown-6 (DSADB18C6). We assessed its performance in isolating Pb(II) by employing stable lead and optimizing the parameters of the extraction system. The results showcased an exceptional ability to extract Pb(II) efficiently. Within 10 minutes, using 20 mmol of DSADB18C6 and under conditions of 10 mg L−1 lead concentration (HNO3 = 0.5 mol L−1), the extraction efficiency reached up to 96.1%. Even after four rounds of stripping with 0.4 mol L−1 ammonium citrate, the efficiency remained at 90.2%. Moreover, the extraction stoichiometry and thermodynamics revealed that DSADB18C6 exhibited superior extraction performance compared to the commercial extractant 4′,4′′,(5′′)-di-(tert-butyldicyclohexano)-18-crown-6 (DtBuDC18C6), in line with the density functional theory (DFT) calculation result. Furthermore, we successfully separated 212Pb from the thorium nitrate solution, maintaining radioactive equilibrium with its progeny. Gamma-spectroscopy confirmed a recovery yield of extraction exceeding 85.7%. This study presents a viable approach, underscoring the potential of DSADB18C6 as a promising extractant for the effective separation of 212Pb from radioactive thorium sources. [ABSTRACT FROM AUTHOR]

Understanding factors that influence the volatility of lanthanide complexes remains an important goal for applications such as gas-phase f-metal separations and the synthesis of lanthanide-containing thin films. Lanthanide complexes often exhibit volatility differences that depend on the ability of ligands to saturate the lanthanide coordination sphere and attenuate intermolecular bonding in the solid state. This can make it difficult to assess how electronic factors associated with differing ligand substituents influence volatility. Here we describe the synthesis, structures, and thermal properties of a series of volatile lanthanide complexes (Ln = Nd, Er, and Yb) containing N4O3 ligands decorated with different alkyl and fluoroalkyl substituents (CF3, CF2CF2CF3, Me, and tBu). These ligands completely enveloped the tested lanthanides to form monomeric complexes with 7-coordinate distorted capped octahedral coordination geometries, as determined using single-crystal X-ray diffraction. Thermogravimetric analysis and bulk sublimation studies show how metal encapsulation affords complexes with the same volatility regardless of metal size, even with lanthanide ions with significantly different radii such as Nd3+ and Yb3+. Most notably, the results show that increasing ligand fluorination, a strategy often used to increase the volatility of metal complexes, is not always beneficial and can significantly attenuate the volatility of lanthanide complexes depending on location with respect to other substituents in the ligand framework. A pair-wise model based on density functional theory shows that the net intermolecular interactions in the unit cell can still be stronger when fluorination is present. In other words, even if individual interactions between neighboring molecules are weaker, the total number of interactions in the solid arising from the nature of crystal packing is equally important to consider. [ABSTRACT FROM AUTHOR]

Valence tautomerism (VT) involves the stimulated reversible intramolecular electron transfer between a redox-active metal and ligand. Dinuclear cobalt complexes bridged by bis(dioxolene) ligands can undergo thermally-induced VT with access to {CoIII-cat-cat-CoIII}, {CoIII-cat-SQ-CoII} and {CoII-SQ-SQ-CoII} states (cat2− = catecholate, SQ˙− = semiquinonate, CoIII refers to low spin CoIII, CoII refers to high spin CoII). The resulting potential for two-step VT interconversions offers increased functionality over mononuclear examples. In this study, the bis(dioxolene) ligand 3,3′,4,4′-tetrahydroxy-5,5′-dimethoxy-benzaldazine (thMH4) was paired with Mentpa (tpa = tris(2-pyridylmethyl)amine, n = 0–3 corresponds to methylation at 6-position of the pyridine rings) to afford [{Co(Mentpa)}2(thM)](PF6)2 (1a, n = 0; 2a, n = 2; 3a, n = 3). Structural, magnetic susceptibility and spectroscopic data show that 1a and 3a remain in the temperature invariant {CoIII-cat-cat-CoIII} and {CoII-SQ-SQ-CoII} forms in the solid state, respectively. In contrast, 2a exhibits incomplete thermally-induced VT between these two tautomeric forms via the mixed {CoIII-cat-SQ-CoII} tautomer. In solution, room temperature electronic absorption spectra are consistent with the assignments from the solid-state, with VT observed only for 2a. From electrochemistry, the proximity of the two 1e−-processes for the thMn− ligand indicates weak electronic communication between the two dioxolene units, supporting the potential for a two-step VT interconversion in thMn− containing complexes. Comparison of the redox potentials of the Co and thMn− processes suggests that only 2a has these processes in sufficient proximity to afford the thermally-induced VT observed experimentally. Density functional theory calculations are consistent with the prerequisite energy ordering for a two-step transition for 2a, and temperature invariant {CoIII-cat-cat-CoIII} and {CoII-SQ-SQ-CoII} states for 1a and 3a, respectively. This work presents the third example, and the first formally conjugated example, of a bridging bis(dioxolene) ligand that can afford two-step VT in a Co complex, suggesting new possibilities towards applications based on multistep switching. [ABSTRACT FROM AUTHOR]

The actinyl tetrachloro complex [An(V / VI)O2Cl4]2−/3− tends to form discrete molecular units in both solution and solid state materials, but related aquachloro complexes have been observed as both discrete coordination compounds and 1-D chain topologies. Subtle differences in the inner sphere coordination significantly influence the formation of structural topologies in the actinyl chloride system, but the exact reasoning for these variations has not been delineated. In the current study, we present the synthesis, structural characterization, and vibrational analysis of two 1-D neptunyl(V) chain compounds: (CH6N3)2[NpO2Cl3] (Np-Gua) and Rb[NpO2Cl2(H2O)] (Np-Rb). Bonding and non-covalent interactions (NCIs) in the systems were evaluated using periodic Density Functional Theory (DFT) to link these properties to related phases. We observed ∼6.5% and ∼3.9% weakening of Np＝O bonds in Np-Gua and Np-Rb compared to the reference Cs3[NpO2Cl4]. NCI analysis distinguished specific assembly modes, where Np-Gua was connected via hydrogen bonding (N–H⋯Cleq and N–H⋯Oyl) and Np-Rb contained both cation interactions (Rb+⋯Oyl and Rb+⋯Cleq) and hydrogen bonding (Oeq–H⋯Oyl) networks. Thermodynamically viable formation pathways for both compounds were explored using DFT methodology. The [NpO2Cl4](aq)3− and [NpO2Cl3(H2O)](aq)2− substructures were identified as precursors to Np-Gua and [NpO2Cl3(H2O)](aq)2− and [NpO2Cl2(H2O)2](aq)− were isolated as the primary building units of Np-Rb. Finally, we utilized DFT to analyze the vibrational modes for Np-Gua and Np-Rb, where we found evidence of the Np＝O bond weakening within the Np(V) chain structures compared to [NpO2Cl4]3−. [ABSTRACT FROM AUTHOR]

Tripodal tetradentate N donor ligands stabilise the most active ATRP catalyst systems. Here, we set out to synthesise the new guanidine ligand TMG-4NMe2uns-penp, inspired by p-substituted tris(2-pyridylmethyl)amine (TPMA) ligands. The impact of changing pyridine against guanidine donors was examined through solid state and solution experiments and density functional theory (DFT) calculations. In the solid state, the molecular structures of copper complexes based on the ligands TMG-4NMe2uns-penp, TMG-uns-penp and TMG3tren were discussed concerning the influence of a NMe2 substituent at the pyridines and the guanidine donors. In solution, the TMG-4NMe2uns-penp system was investigated by several methods, including UV/Vis, EPR and NMR spectroscopy indicating similar properties to that of the highly active TPMANMe2 system. The redox potentials were determined and related to the catalytic activity. Besides the expected trends between these and the ligand structures, there is evidence that guanidine donors in tripodal ligand systems lead to a better deactivation and possibly a faster exchange within the ATRP equilibrium than TPMA systems. Supported by DFT calculations, it derives from an easier cleavable Cu–Br bond of the copper(II) deactivator species. The high activity was stated by a controlled initiator for continuous activator regeneration (ICAR) ATRP of styrene. [ABSTRACT FROM AUTHOR]

Three chitosan ionic liquid type Schiff bases (CS-IL-SBs) were synthesized by grafting three aldehydes (vanillin, cinnamaldehyde, and pyridine-4-carboxaldehyde) on CS-IL (chitosan grafted with p-toluene sulfonic acid) through a Schiff base reaction. Thermogravimetric analysis indicated that the thermal stability of CS was enhanced by the modification of IL and Schiff base groups. All CS-IL-SBs present a non-crystalline structure as analyzed using X-ray diffraction technique and have a positively charged surface in solution for improved dispersion stability as analyzed using zeta potential testing. A corrosion inhibition performance investigation using electrochemical and mass loss methods was undertaken, which were supported with surface analysis and computational studies. All the CS-IL-SBs act as effective corrosion inhibitors obeying Langmuir adsorption isotherm containing both chemisorption and physisorption for N80 steel in 15% HCl solution. Among them, CS-IL-Vin (grafted by vanillin) exhibits a maximum inhibition efficiency of 83.66% at 400 mg L−1. The analysis of the corroded metal surface via scanning electron microscopy depicts a considerably smooth morphology in the presence of adsorbed CS-IL-SBs. Contact angle tests indicated that the water-repellent ability of the metal surface was increased by the addition of CS-IL-SBs. Density functional theory calculations indicated that the active regions of CS-IL-SBs are mainly distributed in –SO3−, benzene rings, and Schiff base groups. Molecular dynamics simulations show that CS-IL-SBs are parallelly adsorbed on the metal surface to form a stable protective film. CS-IL-Vin shows the best performance among the three CS-IL-SBs, which was selected to be compounded with aided inhibitors with different electrical properties. When CS-IL-Vin was compounded with negatively charged 3-carboxybenzene sulfonate in a ratio of 1 : 3, corrosion inhibition efficiency was the highest, reaching 93.45%. [ABSTRACT FROM AUTHOR]

The electrocatalytic CO2 reduction reaction (CO2RR) offers a fascinating approach to converting CO2 into valuable chemical feedstocks. Up to now, the development of highly efficient electrocatalysts has been a significant bottleneck in this field. In this study, employing density functional theory (DFT) calculations, we design a range of stable two-dimensional (2D) metalloporphyrin organic frameworks (TM-PMOFs, TM = Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, and Ag, respectively) built by copper clusters and metalloporphyrin (TM-TCPP), whose CO2RR performance is studied in detail. Among them, the 2D cobaltporphyrin-based organic framework (Co-PMOF) is identified to be the best CO2RR electrocatalyst on account of its low limiting potential (−0.53 V), whose enhanced electrocatalytic performance can be attributed to the presence of numerous active sites on both sides of its 2D framework, as well as the synergistic effect between copper clusters and cobaltporphyrins in facilitating CO2 reduction. These findings provide valuable insights and encourage further experimental research on metallic 2D PMOF materials for CO2 electrochemical reduction. [ABSTRACT FROM AUTHOR]