Latest ArticlesThe concise syntheses of eight 13-methylprotoberberine (13-MePB) and eight enantioenriched 13-methyltetrahydroprotoberberine (13-MeTHPB) alkaloids have been achieved in a tactically modular fashion. This synthetic work features a one-pot metal-free Pictet-Spengler/Friedel-Crafts hydroxyalkylation/dehydration/oxidation sequence and a following highly enantioselective Ir-catalyzed hydrogenation. Given such brevity and modularity, our developed synthetic route would be greatly beneficial to the efficient syntheses of existing natural products and new fully synthetic variants of 13-MePB and 13-MeTHPB family.
By using a perylene diimine (PDI) syn-atropisomer as highly preorganized precursor, we successfully constructed a visible-light-active organic macrocycle PDI-M. The formation of macrocyclic structure effectively avoids self-aggregation of PDI cores and enhances the absorption in visible region. As a photocatalyst, PDI-M exhibits excellent activity on aerobic selective oxidation of sulfide into sulfoxide under visible light irradiation at room temperature. Mechanism studies show that both superoxide and singlet oxygen act as reactive oxygen species. This work provides a typical case toward the maximum utilization of photosensitive groups under mild conditions.
Nanoscale low-dimensional chiral architectures are increasingly receiving scientific interest, because of their potential applications in many fields such as chiral recognition, separation and transformation. Using 6, 12-dibromochrysene (DBCh), we successfully constructed and characterized the large-area two-dimensional chiral networks on Au(111) and one-dimensional metal-liganded chiral chains on Cu(111) respectively. The reasons and processes of chiral transformation of chiral networks on Au(111) were analyzed. We used scanning tunneling spectroscopy (STS) to analyze the electronic state information of this chiral structure. This work combines scanning tunneling microscopy (STM) with non-contact atomic force microscopy (nc-AFM) techniques to achieve ultra-high-resolution characterization of chiral structures on low-dimensional surfaces, which may be applied to the bond analysis of functional nanofilms. Density functional theory (DFT) was used to simulate the adsorption behavior of the molecular and energy analysis in order to verify the experimental results.
Understanding and establishing the structure-activity relation of nanoparticles is a prerequisite for rational design of high-performance electrocatalysts. Cu2O nanoparticles enclosed with different crystal facets, namely, o-Cu2O NPs with {111} facets, c-Cu2O NPs with {100} facets are prepared and their electrocatalytic properties for oxygen evolution reaction (OER) in alkaline condition are evaluated at single nanoparticle level with a combination of scanning electrochemical cell microscopy and scanning electron microscopy. It is found that the o-Cu2O NPs have significantly superior OER electrocatalytic activity compared to c-Cu2O, which is almost inert. The estimated turnover frequency (TOF) at 1.97 V vs. RHE on {111} facet increases from 4 s−1 to 115 s−1 with the octahedron edge length decreasing from 1.3 µm to 100 nm. Deposition of carbon on c-Cu2O surface barely promotes the activity, suggesting the inherent poor electric conductivity within the nanocrystal is most likely the reason for low activity. This work provides direct probing to single transition metal oxide crystals with dramatically different activity.
Two-dimensional polymers (2DPs) are emerging crystalline 2D organic material comprising free-standing, single-atom/monomer-thick, planar, and covalent networks with long-ranging structural order. Benefiting from their intrinsic porosity, crystallinity, and electrical properties, 2DPs have displayed great potential for separation, energy conversion and electronic fields. In this mini review, we aim to provide the recent progress in crystalline 2DPs films form synthesis strategies to characterization methods, as well as the future trends. We first present the synthesis strategy of single-crystalline 2DPs films including crystal engineering approaches and surface science. Also, we summarize the characterization methods of 2DPs films and highlight the advantages and limitations of different methods focusing on chemical bonding, morphology, and crystal structure. Finally, we will present the current challenges and trends regarding the future developments of crystallinity, monomer design, synthesis strategy and characterization.
In the design of conjugated molecules, modular production enables materials to easily realize structure modification and precisely tune their photoelectrical property. Construction of a novel and universal building block is crucial to design and manufacture high performance and stable conjugated molecules for optoelectronic application. Herein, we originally demonstrated a universal 4-qualifiable fluorene-based building block, which is a fundamental molecular segment to functionalize and obtain novel conjugated materials. Compared to the traditional modification at 9-site, additional 4-position functionalization provided an exciting blueprint to not only tune electronic structure and excited state via p-n molecular design engineering and space charge-transfer strategy, but also allow for optimizing intermolecular arrangement and obtaining solution-processing ability. The introduction of the 4-site substituent in fluorene based semiconductors may endow materials with unique properties. Finally, we successfully prepared two stable deep-blue light-emitting conjugated polymer, PODOPF and PODOF, by utilizing the 4-substituent fluorene based building block. It is believable that the performance, stability and processibility of reported outstanding fluorene-based conjugated molecules can be further optimized based on this universal building block.
Herein, we report a highly efficient versatile synthetic route to Chiraphos derivatives through Rh/Ph-bod catalyzed asymmetric addition of aryl boronic acids to phosphinyl dienes. Various substituted phosphinyl dienes, both on the parent skeleton and the phosphine atoms, were well tolerated with this method and provided chiral phosphine oxides in satisfied yield and up to 95% ee. The corresponding Chiraphos derivative displayed an advantage over Chiraphos in the representative Pd-catalyzed asymmetric 1,4-addition reaction.
Herein, we report a borane-promoted reductive deoxygenation coupling reaction to synthesize sulfides. This reaction features excellent functional group compatibility, high efficiency, broad substrate scope, and application in late-stage functionalization of biomolecules. Preliminary mechanistic studies suggest diaryl sulfides are the intermediates of this reaction. Moreover, the real active aryl sulfide anions may be generated in situ with the aid of B2pin2 and react with alkyl tosylates through a concerted SN2 pathway.
Although surface-enhanced Raman spectroscopy (SERS) has been applied for gathering fingerprint information, even in single molecule analysis, the decayed Raman signals in aqueous solutions largely obstruct the on-site insight reaction process. In this study, large-scaled semiconductor films with multi-walled (TiO2/WO3/TiO2) nanopore distribution are fabricated by combining electrochemical anodization and sputtering technique, and then employed as the SERS substrates for detection of molecules at the solid/liquid interfaces. Given the remarkably improved electrochromic property of the multi-walled film, such SERS substrates were endowed with tunable oxygen vacancy (VO) density and distribution via simply applying electrochemical bias voltage, which enabled one to achieve an enhanced charge transfer efficiency and thus a remarkably increased Raman signal even in solution. The VO-rich SERS substrate is highly repeatable, thus providing a reliable platform for in-situ monitoring of the target molecules or intermediates at the solid/liquid interfaces.
Protecting clusters from coalescing by ligands has been universally adopted in the chemical synthesis of atomically precise clusters. Apart from the stabilization role, the effect of ligands on the electronic properties of cluster cores in constructing superatoms, however, has not been well understood. In this letter, a comprehensive theoretical study about the effect of an organic ligand, methylated N-heterocyclic carbene (C5N2H8), on the geometrical and electronic properties of the aluminum-based clusters XAl12 (X = Al, C and P) featuring different valence electron shells was conducted by utilizing the density functional theory (DFT) calculations. It was observed that the ligand can dramatically alter the electronic properties of these aluminum-based clusters while maintaining their structural stability. More intriguingly, different from classical superatom design strategies, the proposed ligation strategy was evidenced to possess the capability of remarkably reducing the ionization potentials (IP) of these clusters forming the ligated superalkalis, which is regardless of their shell occupancy. The charge transfer complex formed during the ligation process, which regulates the electronic spectrum through the electrostatic Coulomb potential, was suggested to be responsible for such an IP drop. The ligation strategy highlighted here may provide promising opportunities in realizing the superatom synthesis in the liquid phase.
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