ChemInform Abstract: Theoretical Study on the Assembly and Stabilization of a Magic Cluster Al4N‐

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Reactions of Group V Metal Atoms with Hydrogen Sulfide:Argon Matrix Infrared Spectra and Theoretical Calculations

The reaction of laser-ablated vanadium, niobium and tantalum atoms with hydrogen sulfide has been investigated using matrix isolation FTIR and theoretical calculations. The metal atoms inserted into the H-S bond of H₂S to form the HMSH molecules (M=V, Nb, Ta), which rearranged to H₂MS molecules on annealing for Nb and Ta. The HMSH molecule can also further react with another H₂S to form the H₂M(SH)₂ molecules. These new molecules were identified on the basis of the D₂S and H₂³⁴S isotopic substitutions. DFT (B3LYP and BPW91) theoretical calculations are used to predict energies, geometries, and vibrational frequencies for these novel metal dihydrido complexes and molecules. Reaction mechanism for formation of group V dihydrido complex was investigated by DFT internal reaction coordinate calculations. The dissociation of HVSH gave VS+H₂ on broad band irradiation and reverse reaction happened on annealing. Based on B3LYP calculation releasing hydrogen from HVSH is endothermic only by 13.5 kcal/mol with lower energy barrier of 16.9 kcal/mol.     

过渡金属类立方烷原子簇化合物电子结构和二阶非线性光学性质的密度泛函理论研究

采用基于第一原理的含时密度泛函理论(TDDFT)对一系列具有类立方烷簇芯结构的过渡金属簇合物二阶非线性光学性质进行了研究。结果证明, 由于簇芯结构的对称性的影响, 这一类簇分子的二阶非线性光学系数的数值要小于三核欠完整类立方烷体系。通过对电子结构的分析, 发现二阶非线性光学性质主要是由簇芯内电荷的迁移造成的。轨道分析显示, -S原子对于电荷的迁移起主要的传递作用。定域化轨道分析证明簇分子中存在的多中心键有利于簇芯内电荷的迁移。分子模拟的研究表明:虽然类立方烷结构簇分子的值比较小, 但是通过合理的配体设计, 获得具有较大值非线性光学晶体是可能的。     

An Old Reaction with New Results: The Unexpected Formation of a Rare Earth Metal Cluster Containing Six Europium Atoms

Employing a standard protocol for the preparation of a trisbenzoylacetonato europium(III) complex with 4‐bromo benzoylacetone 2 as ligand, a new europium species was synthesized and characterized. The X‐ray crystal structure analysis revealed a new europium cluster consisting of six europiumcentres.     

Electronic Excited States Responsible for Dimer Formation upon UV Absorption Directly by Thymine Strands: Joint Experimental and Theoretical Study

The study addresses interconnected issues related to two major types of cycloadditions between adjacent thymines in DNA leading to cyclobutane dimers (T<>Ts) and (6-4) adducts. Experimental results are obtained for the single strand (dT)(20) by steady-state and time-resolved optical spectroscopy, as well as by HPLC coupled to mass spectrometry. Calculations are carried out for the dinucleoside monophosphate in water using the TD-M052X method and including the polarizable continuum model; the reliability of TD-M052X is checked against CASPT2 calculations regarding the behavior of two stacked thymines in the gas phase. It is shown that irradiation at the main absorption band leads to cyclobutane dimers (T<>Ts) and (6-4) adducts via different electronic excited states. T<>Ts are formed via (1)ππ* excitons; [2 + 2] dimerization proceeds along a barrierless path, in line with the constant quantum yield (0.05) with the irradiation wavelength, the contribution of the (3)ππ* state to this reaction being less than 10%. The formation of oxetane, the reaction intermediate leading to (6-4) adducts, occurs via charge transfer excited states involving two stacked thymines, whose fingerprint is detected in the fluorescence spectra; it involves an energy barrier explaining the important decrease in the quantum yield of (6-4) adducts with the irradiation wavelength.     

Role of Hydrogen Bond Defects for Cluster Formation and Distribution in Ionic Liquids by Means of Neutron Diffraction and Molecular Dynamics Simulations

Defects fundamentally govern the properties of all real materials. Correlating molecular defects to macroscopic quantities remains a challenge, particularly in the liquid phase. Herein, we report the influence of hydrogen bonds (HB) acting as defects in mixtures of non-hydroxyl-functionalized ionic liquids (ILs) with an increasing concentration of hydroxyl-functionalized ILs. We observed two types of HB defects: The conventional HBs between cation and anion (c–a), and the elusive HBs between cations (c–c) despite the repulsive Coulomb forces. We use neutron diffraction with isotopic substitution in combination with molecular dynamics simulations for measuring the geometry, strength, and distribution of mobile OH defects in the IL mixtures. In principle, this procedure allows relating the number and stability of defects to macroscopic properties such as diffusion, viscosity, and conductivity, which are of utmost importance for the performance of electrolytes in batteries and other electrical devices.     

Thermochemistry of Alane Complexes for Hydrogen Storage: A Theoretical and Experimental Investigation

Knowledge of the relative stabilities of alane (AlH(3)) complexes with electron donors is essential for identifying hydrogen storage materials for vehicular applications that can be regenerated by off-board methods; however, almost no thermodynamic data are available to make this assessment. To fill this gap, we employed the G4(MP2) method to determine heats of formation, entropies, and Gibbs free energies of formation for 38 alane complexes with NH(3-n)R(n) (R = Me, Et; n = 0-3), pyridine, pyrazine, triethylenediamine (TEDA), quinuclidine, OH(2-n)R(n) (R = Me, Et; n = 0-2), dioxane, and tetrahydrofuran (THF). Monomer, bis, and selected dimer complex geometries were considered. Using these data, we computed the thermodynamics of the key formation and dehydrogenation reactions that would occur during hydrogen delivery and alane regeneration, from which trends in complex stability were identified. These predictions were tested by synthesizing six amine-alane complexes involving trimethylamine, triethylamine, dimethylethylamine, TEDA, quinuclidine, and hexamine and obtaining upper limits of ΔG° for their formation from metallic aluminum. Combining these computational and experimental results, we establish a criterion for complex stability relevant to hydrogen storage that can be used to assess potential ligands prior to attempting synthesis of the alane complex. On the basis of this, we conclude that only a subset of the tertiary amine complexes considered and none of the ether complexes can be successfully formed by direct reaction with aluminum and regenerated in an alane-based hydrogen storage system.     

担载三核羰基钴簇的合成,表征和烯烃氢甲酰化反应

通过配体交换反应合成了膦化硅胶担载的羰基钴簇配合物(Si)—PPh_2[BrCCo_3(CO)_(9-2)],用IR、XPS和DPS对其结构进行了表征,并测得了担载簇配合物的金属含量,研究了担载簇(Si)—PPh_2[BrCCo_3(CO)_(9-2)]在烯烃氢甲酰化反应中的催化活性.结果表明,担载的三核羰基钴簇可达到与均相三核钴簇基本一致的反应活性,在一定的反应条件下,烯烃转化率和醇醛收率均在85％以上,有很少量的加氢产物生成。     

Theoretical Study on Electronic,Optical, and Charge Transfer Properties of Starburst Triphenylamine as Sensibilizer @TiO_2 Cluster for Dye-sensitized Solar Cells

Here, a series of starburst triphenylamine(WD8) derivatives for dye-sensitized solar cells(DSSCs) applications have been designed. The frontier molecular orbitals(FMOs) property, absorption spectra, and charge transfer rate property of WD8 and its derivatives were simulated. We also evaluated the FMOs energies and absorption spectra of WD8 and its derivatives with the TiO2 cluster. The simulation results show that the phenothiazine-triphenylamine and 2-cyanoacetic acid groups in the ortho-position will increase the HOMO energy, decrease the LUMO energy, and narrow the HOMO-LUMO gap of WD8. The charge injection from WD8 and its derivatives to TiO2 should be more favorable. The phenothiazine-triphenylamine and 2-cyanoacetic acid groups in the ortho-position will decrease the electron and hole injection barriers of WD8. The phenothiazinetriphenylamine and 2-cyanoacetic acid groups in the ortho-position will improve the absorption spectra properties of WD8. The absorption spectra of WD8 and its derivatives with the TiO2 cluster would have a red shift. The phenothiazine-triphenylamine and 2-cyanoacetic acid groups in the ortho-position will increase the charge transfer property of WD8.     

The Mass Spectra of 4-(3-Arylsydnonyl)Methanols and Their Derivatives: Formation of Ar-N=C-H Cation via a Hydrogen Migration

Fourteen mass spectra of the sydnonylmethanols and their derivatives have been measured under EI conditions. The process of losing a OR' radical and hydrogen migration reaction are accompanyed with lost of a CO and an NO channel. The competition between cleavage of C-0 bond and hydrogen migration is mainly controlled by the type and size of the R' group.     

Intramolecular Hydrogen Bonding Enables a Zwitterionic Mechanism for Macrocyclic Peptide Formation: Computational Mechanistic Studies of CyClick Chemistry

Macrocyclic peptides have become increasingly important in the pharmaceutical industry. We present a detailed computational investigation of the reaction mechanism of the recently developed “CyClick” chemistry to selectively form imidazolidinone cyclic peptides from linear peptide aldehydes, without using catalysts or directing groups (Angew. Chem. Int. Ed. 2019 , 58, 19073–19080). We conducted computational mechanistic to investigate the effects of intramolecular hydrogen bonds (IMHBs) in promoting a kinetically facile zwitterionic mechanism in “CyClick” of pentapeptide aldehyde AFGPA. Our DFT calculations highlighted the importance of IMHB in pre-organization of the resting state, stabilization of the zwitterion intermediate, and the control of the product stereoselectivity. Furthermore, we have also identified that the low ring strain energy promotes the “CyClick” of hexapeptide aldehyde AAGPFA to form a thermodynamically more stable 15+5 imidazolidinone cyclic peptide product. In contrast, large ring strain energy suppresses “CyClick” reactivity of tetra peptide aldehyde AFPA from forming the 9+5 imidazolidinone cyclic peptide product.     

To a Theory of Electrocatalysis for the Hydrogen Evolution Reaction: The Hydrogen Chemisorption Energy on the Transition Metal Alloys within the Anderson–Newns Model

Estimates of the energy of chemisorption of hydrogen (ECH) on a number of alloys of transition metals that are of interest from the viewpoint of a theory of electrocatalysis are made within the Anderson–Newns model. As a simplest example, the behavior of ECH as a function of the position of the Fermi level of a system for nickel containing admixtures of simple metals is studied in a fixed-band approximation. As alternative examples, where this approximation is not fulfilled, a calculation of ECH on tungsten carbide and a Pd_{1 – x} Ag _x alloy is performed. It is shown that agreement between calculated ECH and observed ECH is reached in the case of an Ni_{1 – x} Cu _x alloy after taking into account mutual influence of processes of adsorption and segregation on the alloy surface. Dependence of rates of a number of electrochemical reactions on the composition and electronic structure of alloys is discussed for all the alloys considered and a comparison with experiment is performed.     

Bond Dissociation Energies and Electronic Structures in a Series of Peroxy Radicals: A Theoretical Study

Quantum chemical calculations are performed to estimate the bond dissociation energies (BDEs) for 18 peroxy radicals. Since DFT methods are researched to have low basis sets sensitivity, these radicals are studied by utilizing the hybrid density functional theory (DFT) (B3LYP, B3P86, B3PW91 and PBE1PBE) in conjunction with the 6‐311G** basis set and the complete basis set (CBS‐Q) method. On the basis of comparisons of the computational results and the experimental values, we evaluate the effectiveness of above methods. It is demonstrated that CBS‐Q method is the best method for computing the reliable BDEs of C—OO bond, with the average absolute errors of 2.1 kcal/mol. So CBS‐Q method is suitable to predict accurate BDEs of C‐OO bond for peroxy compounds. The computational energy gaps between the HOMO and LUMO of studied compounds are almost identical from the point of view of stability and substantial HOMO‐LUMO gaps for all molecules suggest their electronic stability. In addition, substituent effect on the C—OO BDE of peroxy radicals is analyzed. It is noted that the effects of substitution on the C—OO BDE of peroxy radicals are significant. Our results will shed lights on future theoretical and experimental work.     

Benchmarking Three Ruthenium Phosphide Phases for Electrocatalysis of the Hydrogen Evolution Reaction: Experimental and Theoretical Insights

The outstanding electrocatalytic activity of ruthenium (Ru) phosphides toward the hydrogen evolution reaction (HER) has received wide attention. However, the effect of the Ru phosphide phase on the HER performance remains unclear. Herein, a two-step method was developed to synthesize nanoparticles of three types of Ru phosphides, namely, Ru₂P, RuP, and RuP₂, with similar morphology, dimensions, loading density, and electrochemical surface area on graphene nanosheets by simply controlling the dosage of phytic acid as P source. Electrochemical tests revealed that Ru₂P/graphene shows the highest intrinsic HER activity, followed by RuP/graphene and RuP₂/graphene. Ru₂P/graphene affords a current density of 10 mA cm⁻² at an overpotential of 18 mV in acid media. Theoretical calculations further showed that P-deficient Ru₂P has a lower free energy of hydrogen adsorption on the surface than other two, P-rich Ru phosphides (RuP, RuP₂), which confirms the excellent intrinsic HER activity of Ru₂P and is consistent with experiment results. The work reveals for the first time a clear trend of HER activity among three Ru phosphide phases.     

Ti‐Substituted Boranes as Hydrogen Storage Materials: A Computational Quest for the Ideal Combination of Stable Electronic Structure and Optimal Hydrogen Uptake

Hydrogen storage : A family of Ti‐substituted boranes (see figure) having optimum electronic structures and the ability to absorb hydrogen has been designed computationally. Substantial binding energies and gravimetric densities of hydrogen storage show their potential as hydrogen storage materials. The computational study invites experimental synthesis of the novel borane family and offers a guide to searching for new hydrogen storage materials.

     

Heterostructure of Si and CoSe2: A Promising Photocathode Based on a Non‐noble Metal Catalyst for Photoelectrochemical Hydrogen Evolution

Development of a solar water splitting device requires design of a low‐cost, efficient, and non‐noble metal compound as alternative to noble metals. For the first time, we showed that CoSe₂ can function as co‐catalyst in phototoelectrochemical hydrogen production. We designed a heterostructure of p‐Si and marcasite‐type CoSe₂ for solar‐driven hydrogen production. CoSe₂ successively coupled with p‐Si can act as a superior photocathode in the solar‐driven water splitting reaction. Photocurrents up to 9 mA cm^?2 were achieved at 0 V vs. reversible hydrogen electrode. Electrochemical impedance spectroscopy showed that the high photocurrents can be attributed to low charge transfer resistance between the Si and CoSe₂ interfaces and that between the CoSe₂ and electrolyte interfaces. Our results suggest that this CoSe₂ is a promising alternative co‐catalyst for hydrogen evolution.