A theoretical investigation of Zn?Zn and Be?Be one electron bond

Attachment of one electron to 1,2-diBeX-benzene and 1,2-diZnX-benzene derivatives leads to the formation of stronger Be Be and Zn Zn interaction compared to the neutral one. This is reflected in the dramatic shortening of the Be Be and Zn Zn distance. The formation of these 2-center-1-electron bonds have also been confirmed by topological survey of electron density using quantum theory of atoms in molecules and electron localization function. The formation of these bonds is expected to render stability to these radical anions. These radical anions are stable toward electron detachment and computed bond dissociation energy values are also significant.     

Epitaxial growth of borophene on substrates

Borophene, a two-dimensional (2D) planar boron sheet, has attracted dramatic attention for its unique physical properties that are theoretically predicted to be different from those of bulk boron, such as polymorphism, superconductivity, Dirac fermions, mechanical flexibility and anisotropic metallicity. Nevertheless, it has long been difficult to obtain borophene experimentally due to its susceptibility to oxidation and the strong covalent bonds in bulk forms. With the development of growth technology in ultra-high vacuum (UHV), borophene has been successfully synthesized by molecular beam epitaxy (MBE) supported by substrates in recent years. Due to the intrinsic polymorphism of borophene, the choice of substrates in the synthesis of borophene is pivotal to the atomic structure of borophene. The different interactions and commensuration of borophene on various substrates can induce various allotropes of borophene with distinct atomic structures, which suggests a potential approach to explore and manipulate the structure of borophene and benefits the realization of novel physical and chemical properties in borophene due to the structure–property correspondence. In this review, we summarize the recent research progress in the synthesis of monolayer (ML) borophene on various substrates, including Ag(1 1 1), Ag(1 1 0), Ag(1 0 0), Cu(1 1 1), Cu(1 0 0), Au(1 1 1), Al(1 1 1) and Ir(1 1 1), in which the polymorphism of borophene is present. Moreover, we introduce the realization of bilayer (BL) borophene on Ag(1 1 1), Cu(1 1 1) and Ru(0 0 0 1) surfaces, which possess richer electronic properties, including better thermal stability and oxidation resistance. Then, the stabilization mechanism of polymorphic borophene on their substrates is discussed. In addition, experimental investigations on the unique physical properties of borophene are also introduced, including metallicity, topology, superconductivity, optical and mechanical properties. Finally, we present an outlook on the challenges and prospects for the synthesis and potential applications of borophene.     

How deeply are core electrons perturbed when valence electrons are spin polarized? The case study of transition metal compounds

The ferromagnetic and antiferromagnetic wave functions of the KMnF₃ perovskite have been evaluated quantum-mechanically by using an all electron approach and, for comparison, pseudopotentials on the transition metal and the fluorine ions. It is shown that the different number of α and β electrons in the d shell of Mn perturbs the inner shells, with shifts between the α and β eigenvalues that can be as large as 6 eV for the 3s level, and is far from negligible also for the 2s and 2p states. The valence electrons of F are polarized by the majority spin electrons of Mn, and in turn, spin polarize their 1s electrons. When a pseudopotential is used, such a spin polarization of the core functions of Mn and F can obviously not take place. The importance of such a spin polarization can be appreciated by comparing (i) the spin density at the Mn and F nuclear position, and then the Fermi contact constant, a crucial quantity for the hyperfine coupling, and (ii) the ferromagnetic–antiferromagnetic energy difference, when obtained with an all electron or a pseudopotential scheme, and exploring how the latter varies with pressure. This difference is as large as 50% of the all electron datum, and is mainly due to the rigid treatment of the F ion core. The effect of five different functionals on the core spin polarization is documented.     

Fine Pore-Structure Engineering by Ligand Conformational Control of Naphthalene Diimide-Based Semiconducting Porous Coordination Polymers for Efficient Chemiresistive Gas Sensing

Exploring new porous coordination polymers (PCPs) that have tunable structure and conductivity is attractive but remains challenging. Herein, fine pore structure engineering by ligand conformation control of naphthalene diimide (NDI)-based semiconducting PCPs with π stacking-dependent conductivity tunability is achieved. The π stacking distances and ligand conformation in these isoreticular PCPs were modulated by employing metal centers with different coordination geometries. As a result, three conjugated PCPs (Co−pyNDI, Ni−pyNDI, and Zn−pyNDI) with varying pore structure and conductivity were obtained. Their crystal structures were determined by three-dimensional electron diffraction. The through-space charge transfer and tunable pore structure in these PCPs result in modulated selectivity and sensitivity in gas sensing. Zn−pyNDI can serve as a room-temperature operable chemiresistive sensor selective to acetone.     

Nucleus Independent Chemical Shift (NICS) at Small Distances from the Molecular Plane: The Effect of Electron Density

When close to the molecular plane, the behavior of nucleus independent chemical shift (NICS) as a function of the distance from the molecular plane deviates from its behavior at larger distances. By using a dense grid of NICS-probes (BQs) it is shown that, when close to the molecular plane, maximal (absolute) NICS values are obtained above the atoms. These maxima move towards the center as the grid is elevated until the (absolute) maximum NICS is obtained at the center and stay there when the grid is further elevated. It is shown that this behavior is a result of the current density, which is influenced by the electron density, according to the Biot-Savart law, which, in turn, causes the induced magnetic field measured by the NICS. It is thus concluded that if magnetic aromaticity is studied, the NICS calculations should be carried out at a large enough distance so that only the π-ring current affects the NICS. At distances ≥2 Å, NICS(r)_π,zz=A+B*C^r. Using non-linear correlation for obtaining A, B and C and extrapolate to NICS(1)_π,zz and NICS(1.7)_π,zz is recommended as measures for aromaticity.     

Probing Electronic Symmetry Reduction during Charge Migration via Time-Resolved X-Ray Diffraction

The present work focuses on probing ultrafast charge migration after symmetry-breaking excitation using ultrashort laser pulses. LiCN is chosen as prototypical system because it can be oriented in the laboratory frame and it possesses optically-accessible charge transfer states at low energies. The charge migration is simulated within the hybrid time-dependent density functional theory/configuration interaction framework. Time-resolved electronic current densities and simulated time-resolved x-ray diffraction signals are used to unravel the mechanism of charge migration. Our simulations demonstrate that specific choices of laser polarization lead to a control over the symmetry of the induced charge migration. Moreover, time-resolved x-ray diffraction signals are shown to encode transient symmetry reduction at intermediate times.     

Influence of Changing the Remote Substituents on Charge Transfer Properties of Cyanide-Bridged Trinuclear Fe−Ru−Fe Complexes

To investigate the effect of ligand remote (>10 Å) substituents on the bridging metal center on the metal-to-metal charge transfer (MMCT) properties in cyanidometa-bridged complexes, a series of new cyanidometal-bridged complexes and their one-electron and two-electron oxidation products have been synthesized and well characterized (namely, trans-[Cp(dppe)Fe−NC−(L)Ru(PPh₃)−CN−Fe(dppe)Cp][PF₆]_n (n=2, 3, 4) (L=dmptpy, 1[PF₆]_n ; L=meoptpy, 2[PF₆]_n ; L=t-Buptpy, 3[PF₆]_n ) (Cp=1,3-cyclopentadiene, dppe=1,2-bis(diphenylphosphino)ethane, PPh₃=triphenylphosphine, dmptpy=4′-(4-dimethylaminophenyl)-2,2′,6′,2′′-terpyridine, meoptpy=4′-(4-methoxyphenyl)-2,2′,6′,2′′-terpyridine, t-Buptpy=4′-(4-tertbutylphenyl)-2,2′,6′,2′′-terpyridine)). The investigations suggest that the cyanido-stretching (ν_CN) vibration energy for the complexes is unsensitive to the electron-donating ability change of the remote substituents of the cyanidometal bridging auxiliary ligand from tertbutyl, methoxy to dimethylamino group. However, the MMCT energies of the one- and two-electron oxidation complexes are still sensitive to the remote substituents of the ligand on the bridging metal center, and decreases with the increase of the electron-donating ability of the remote substituents from tertbutyl, methoxy to dimethylamino group. All one-electron and two-electron oxidation products belong to Class II mixed valence compounds according to the classification of Robin and Day.     

Cover Feature: Fluoroalkyl Sulfoximines for Versatile Photocatalytic Radical Fluoroalkylations (Chem. Rec. 9/2023)

Fluoroalkyl sulfoximines, which serve as electron-accepting fluoroalkyl radical sources, are easy-to-handle, solid, and bench-stable chemicals. Fluoroalkyl radicals can be generated from sulfoximine reagents using strong one-electron injectors, such as a highly reducing photoredox catalyst in the excited state. Our group has developed photocatalytic radical di- and mono-fluoromethylation and α-monofluoroalkylation of olefins with the corresponding fluoroalkyl sulfoximines. In this personal account, appropriate combinations of fluoroalkyl sulfoximines and photoredox catalysts, leading to successful radical fluoroalkylation, have been discussed.     

两种功能化纳米金粒子固酶电极的催化性能

以合成的4-巯基苯甲酸功能化纳米金粒子和聚乙烯基吡啶包覆纳米金粒子分别作为固酶载体,制备了2种新型固酶电极,在此基础上组装了2种酶燃料电池。采用电化学方法结合紫外可见分光光度法、透射电镜技术等手段研究了固酶载体的形貌,酶-载体间相互作用对电极表面固定酶分子的光谱学性质,酶-电极间直接电子迁移能力和催化底物反应性能的影响,进一步评估和比较了两种酶燃料电池的能量输出性能。实验结果表明：4-巯基苯甲酸功能化纳米金粒子固酶基电极可以实现酶-电极间的直接电子迁移而且对葡萄糖和氧气具有良好的催化性能(催化反应起始电位分别为-0.03和0.96 V,底物转化频率分别是1.3和0.5 s^-1),其催化性能的重现性、长期使用性能、酸碱耐受性和热稳定性良好,随着自组装固酶层数的增加,催化性能随之增强直至达到极限催化电流;电池性能测试结果表明4-巯基苯甲酸功能化纳米金粒子固酶基燃料电池的开路电压为0.88 V,最大输出能量密度：864.0 μW·cm^-2,长期使用性能优异(储存3 周后仍可达到最佳能量输出的80%以上)。     

Moving toward Ylide‐Stabilized Carbenes

The effect of ylide substitution at the α position to the carbene carbon (C_c) atom on the stability and σ‐donating ability of a number of cyclic carbenes has been studied theoretically. The stabilities of all of the carbenes were investigated from an evaluation of their singlet–triplet energy gaps and stabilization energies. All carbenes were found to have a stable singlet state. The energy of the σ‐symmetric lone‐pair orbital at the C_c atom increases as a result of the introduction of ylide centers near to the C_c atom. This indicates an enhanced σ‐donating ability of the ylide‐containing carbenes. The calculated carbonyl‐stretching frequencies of the corresponding rhodium complexes, proton affinities, and nucleophilicity index values correlate well with the σ basicity of the carbenes.