Investigation of mononuclear,dinuclear, and trinuclear transition metal (II) complexes derived from an asymmetric Salamo‐based ligand possessing three different coordination modes

A new asymmetric Salamo‐based ligand H₂L was synthesized using 3‐tert‐butyl‐salicylaldehyde and 6‐methoxy‐2‐[O‐(1‐ethyloxyamide)]‐oxime‐1‐phenol. By adjusting the ratio of the ligand H₂L and Cu (II), Co (II), and Ni (II) ions, mononuclear, dinuclear, and trinuclear transition metal (II) complexes, [Cu(L)], [{Co(L)}₂], and [{Ni(L)(CH₃COO)(CH₃CH₂OH)}₂Ni] with the ligand H₂L possessing completely different coordination modes were obtained, respectively. The optical spectra of ligand H₂L and its Cu (II), Co (II) and Ni (II) complexes were investigated. The Cu (II) complex is a mononuclear structure, and the Cu (II) atom is tetracoordinated to form a planar quadrilateral structure. The Co (II) complex is dinuclear, and the two Co (II) atoms are pentacoordinated and have coordination geometries of distorted triangular bipyramid. The Ni (II) complex is a trinuclear structure, and the terminal and central Ni (II) atoms are all hexacoordinated, forming distorted octahedral geometries. Furthermore, optical properties including UV–Vis, IR, and fluorescence of the Cu (II), Co (II), and Ni (II) complexes were investigated. Finally, the antibacterial activities of the Cu (II), Co (II), and Ni (II) complexes were explored. According to the experimental results, the inhibitory effect was found to be enhanced with increasing concentrations of the Cu (II), Co (II), and Ni (II) complexes.     

Pentapnictogen heterocyclic monoanions: Structure,stability, and aromaticity

Inorganic planar ring-shape molecules with 4n + 2 π electrons are always the focus of experimental synthesis and theoretical research due to their potential aromaticity and stability. In this work, the whole series of five-membered heterocycle monoanions X _nY_5-n⁻ (X, Y = group 15 elements; n = 1-4) were thoroughly investigated by means of density functional theory calculations. They all have large formation energies and HOMO-LUMO gap energies, suggesting the potential thermodynamic and kinetic stability. Their aromaticities are comparable to that of typical aromatic hydrocarbons. Their thermal stabilities were firmly established by the ab initio molecular dynamics simulations. As most of them are predicted for the first time, their various spectra were simulated for experimental characterization. Furthermore, we demonstrate that these five-membered cyclic anions can be employed as η⁵-ligand to construct novel all-inorganic metallocenes, which may serve as the building blocks of low-dimensional nanomaterials.     

Dimeric Manganese-Catalyzed Hydroarylation and Hydroalkenylation of Unsaturated Amides

An unprecedented Mn(I)-catalyzed selective hydroarylation and hydroalkenylation of unsaturated amides with commercially available organic boronic acids is reported. Alkenyl boronic acids have been successfully employed for the first time in Mn(I)-catalyzed carbon–carbon bond formation. A wide array of β-alkenylated amide products can be obtained in moderate to good yields, which offers practical access to five- and six-membered lactams. This protocol has predictable regio- and chemoselectivity, excellent functional group compatibility and ease of operation in air, representing a significant step-forward towards manganese-catalyzed C−C coupling.     

Efficient Quantum Dot Light-Emitting Diodes Based on Well-Type Thick-Shell CdxZn1−xS/CdSe/CdyZn1−yS Quantum Dots

Device grade quantum dots (QDs) require QDs ensembles to retain their original superior optical properties as in solution. QDs with thick shells are proven effective in suppressing the inter-dot interaction and preserving the emission properties for QDs solids. However, lattice strain–induced defects may form as the shell grows thicker, resulting in a notable photoluminescence quenching. Herein, a well-type Cd_xZn_1−xS/CdSe/Cd_yZn_1−yS QDs is proposed, where ternary alloys CdZnS are adopted to match the lattice parameter of intermediate CdSe by separately adjusting the x and y parameters. The resultant thick-shell Cd_0.5Zn_0.5S/CdSe/Cd_0.73Zn_0.27S QDs reveal nonblinking properties with a high PL QY of 99% in solution and 87% in film. The optimized quantum dot light-emitting diodes (QLEDs) exhibit a luminance of 31547.5 cd m⁻² at the external quantum efficiency maximum of 21.2% under a bias of 4.0 V. The shell thickness shows great impact on the degradation of the devices. The T₅₀ lifetime of the QLEDs with 11.2 nm QDs reaches 251 493 h, which is much higher than that of 6.5 and 8.4 nm QDs counterparts. The performances of the well-type thick-shell QLEDs are comparable to state-of-the-art devices, suggesting that this type of QDs is a promising candidate for efficient optoelectronic devices.     

The visible and ultraviolet organic light-emitting diodes with germanium dioxide as facile solution-processed anode buffer layer

Germanium dioxide (GeO₂) aqueous solutions are facilely prepared and the corresponding anode buffer layers (ABLs) with solution process are demonstrated. Atomic force microscopy, X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy measurements show that solution-processed GeO₂ behaves superior film morphology and enhanced work function. Using GeO₂ as ABL of organic light-emitting diodes (OLEDs), the visible device with tris(8-hydroxy-quinolinato)aluminium as emitter gives maximum luminous efficiency of 6.5 cd/A and power efficiency of 3.5 lm/W, the ultraviolet device with 3-(4-biphenyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole as emitter exhibits short-wavelength emission with peak of 376 nm, full-width at half-maximum of 42 nm, maximum radiance of 3.36 mW/cm² and external quantum efficiency of 1.5%. The performances are almost comparable to the counterparts with poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate) as ABL. The current, impedance, phase and capacitance as a function of voltage characteristics elucidate that the GeO₂ ABL formed from appropriate concentration of GeO₂ aqueous solution favors hole injection enhancement and accordingly promoting device performance.     

Unlocking the Drug Potential of the Bryostatin Family: Recent Advances in Product Synthesis and Biomedical Applications

Bryostatins are a class of naturally occurring macrocyclic lactones with a unique fast developing portfolio of clinical applications, including treatment of AIDS, Alzheimer's disease, and cancer. This comprehensive account summarizes the recent progress (2014–present) in the development of bryostatins, including their total synthesis and biomedical applications. An emphasis is placed on the discussion of bryostatin 1 , the most-studied analogue to date. This review highlights the synthetic and biological challenges of bryostatins and provides an outlook on their future development.     

Fast Liquid Phase Epitaxial Growth for Perovskite Single Crystals

Semiconductors grown by the solution-processed method have shown low-cost,facile fabrication process and comparable performance.However,there are many reasons why it is difficult to achieve high quality films.For example,lattice constant mismatch is one of the problems when photovoltaic devices made of organ metallic perovskites.In this work,MAPbBr^{MA=CH3NH3^+}perovskites single crystals grown on the surface of MAPbBr2.5 CI0.5 perovskites single crystals via liquid epitaxial growth method is demonstrated.It is found that when the lattice constants of the two perovskite single crystals are matched,another crystal can be grown on the surface of one crystal by epitaxial growth.The whole epitaxy growth process does not require high heating temperature and long heating time.X-ray diffraction method is used to prove the lattice plane of the substrate and the epitaxial grown layer.A scanning electron microscope is used to measure the thickness of the epitaxial layer.Compared with perovskite-based photodetectors without epitaxial growth layer,perovskite-based photodetectors with epitaxial growth layer have lower dark current density and higher optical responsibility.     

Et2Zn-mediated stoichiometric C(sp)-H silylation of 1-alkynes and chlorosilanes

A first example of an Et₂Zn mediated silylation of 1-aklynes is reported. A series of functional groups are tolerated in this reaction. Mechanistic studies support Zn alkynilides as intermediates in the reaction. This reaction protocol provides a practical method for the preparation of alkynylsilanes and expands the application of organometallic zinc in organic synthesis.     

原位液相透射电子显微镜及其在 纳米粒子表征方面的应用

近年来,基于透射电子显微技术、微纳加工技术和薄膜制造技术的发展,原位液相透射电子显微技术产生,为构建多种纳米级分辨率尺度下的微实验平台,发展新型纳米表征技术和众多领域的相关研究提供了途径.本文首先介绍了应用于原位液相透射电子显微技术的液体腔设计要求,然后介绍了液体腔的发展和典型的制备工艺,最后综述了近年来液体腔透射电子显微镜在纳米粒子成核和生长方面的应用研究,并探讨了该技术前沿发展面临的机遇和挑战.本文将为提高我国先进纳米表征技术和原子精准构筑技术提供相关讨论和支持.     

Direct Intermediate Regulation Enabled by Sulfur Containers in Working Lithium–Sulfur Batteries

Polysulfide intermediates (PSs), the liquid-phase species of active materials in lithium–sulfur (Li-S) batteries, connect the electrochemical reactions between insulative solid sulfur and lithium sulfide and are key to full exertion of the high-energy-density Li-S system. Herein, the concept of sulfur container additives is proposed for the direct modification on the PSs species. By reversible storage and release of the sulfur species, the container molecule converts small PSs into large organosulfur species. The prototype di(tri)sulfide-polyethylene glycol sulfur container is highly efficient in the reversible PS transformation to multiply affect electrochemical behaviors of sulfur cathodes in terms of liquid-species clustering, reaction kinetics, and solid deposition. The stability and capacity of Li-S cells was thereby enhanced. The sulfur container is a strategy to directly modify PSs, enlightening the precise regulation on Li-S batteries and multi-phase electrochemical systems.