Molecular Engineering Design for High-Performance Aqueous Zinc-Organic Battery

Novel small sulfur heterocyclic quinones(6a,16adihydrobenzo[b]naphtho[2′,3′:5,6][1,4]dithiino[2,3-i]thianthrene-5,7,9,14,16,18-hexaone(4S6Q)and benzo[b]naphtho[2′,3′:5,6][1,4]dithiino[2,3-i]thianthrene-5,9,14,18-tetraone(4S4Q))are developed by molecule structural design method and as cathode for aqueous zincorganic batteries.The conjugated thioether(–S–)bonds as connected units not only improve the conductivity of compounds but also inhibit their dissolution by both extendedπ-conjugated plane and constructed flexible molecular skeleton.Hence,the Zn//4S6Q and Zn//4S4Q batteries exhibit satisfactory electrochemical performance based on 3.5 mol L-1(M)Zn(ClO4)2electrolyte.For instance,the Zn//4S6Q battery obtains 240 and 208.6 mAh g^(-1)of discharge capacity at 150 mA g^(-1)and 30 A g^(-1),respectively.The excellent rate capability is ascribed to the fast reaction kinetics.This system displays a superlong life of 20,000 cycles with no capacity fading at 3 A g^(-1).Additionally,the H+-storage mechanism of the 4S6Q compound is demonstrated by ex situ analyses and density functional theory calculations.Impressively,the battery can normally work at-60℃benefiting from the anti-freezing electrolyte and maintain a high discharge capacity of 201.7 mAh g^(-1),which is 86.2%of discharge capacity at 25℃.The cutting-edge electrochemical performances of these novel compounds make them alternative electrode materials for Zn-organic batteries.

Annulation Cascades of Cyclosulfonium Salts and Alkenes towards Sulfur-Containing N-Heterocycles by Visible Light/Copper Catalysis

Although,great achievements have been made in the synthesis of heterocycles using radical addition/cyclization strategy,developing versatile alkyl radical precursors,especially the non-stabilized long chain alkyl radicals for this strategy still remains a huge challenge.Herein,we report an efficient annulation cascade reaction between cyclosulfonium salts and alkenes for the synthesis of sulfur-containing N-heterocycles by visible light/copper catalysis under mild conditions.The C—S bond cleavage/radical cascade reaction delivers a variety of corresponding N-heterocycles containing aryl alkyl thioether motifs with good functional group tolerance.Significantly,the current system could be used for the late-stage functionalization of complex bioactive molecules.

Metal-Free Synthesis of 2-Aminobenzothiazoles via I2-Catalyzed Tandem Cyclization Reaction of Amines and Carbon Disulfide

Comprehensive Summary,A convenient approach for the construction of 2-aminobenzothiazoles via I2-catalyzed tandem cyclization reaction of amines and carbon disulfide has been developed.The present approach starts from simple and readily available starting materials,affording a series of 2-aminobenzothiazoles in up to 89%yields under metal-free conditions.In this work,C—H/N—H functionalization was achieved and multiple C-hetero bonds were successfully constructed in one pot.

Desulfurization using the 1,2-dimethylimidazolium ionic liquid as an adsorbent

The aim of this study is to investigate the possible use of a 1,2-dimethylimidazolium ionic liquid,2,2-bis（（1,2-dimethylimidazolium）methyl）propane-1,3-diol hexafluorophosphate（1）,as an adsorbent to selectively remove aromatic heterocyclic sulfur compounds from model fuels.The result indicates that adsorbent 1 is insoluble in model fuels.The spent IL saturated sulfur compounds could be regenerated by a water dilution process.The influence of extraction time or temperature as well as the molar ratio of 1 to aromatic heterocyclic sulfur compound was also studied.

Atmospheric pressure gas chromatography-tandem mass spectrometry analysis of fourteen emerging polycyclic aromatic sulfur heterocycles in PM_(2.5)

Research on pollution characteristics and toxicities of emerging polycyclic aromatic sulfur heterocycles(PASHs) in PM_(2.5) has not been reported due to the lack of analytical method with the needed performance.In the present study,a novel method for the determination of 14 PASHs in PM_(2.5) was developed using atmospheric pressure gas chro matography-tandem mass spectrometry(APGC-MS/MS).Atmospheric pressure chemical ionization was operated with multiple reaction monitoring in positive ionization mode.High sensitivity(method detection limit <1.673 pg/m^(3)),acceptable re coveries(67.6%-120.8%) and precisions(RSD of 2.2%-15.4%) were obtained.The method was successfully applied for analyzing PASHs in 10 PM_(2.5) samples collected from Taiyuan,a typical industrial city in China,in 2016,The total concentrations were from 929 pg/m^(3) to 14,593 pg/m^(3).The determined levels indicated that further investigations on environmental fate and toxicities of PM_(2.5)-bound PASHs may be needed.

Facile Synthesis of S-Fused Multi-Membered Polycyclic Heterocycles:A Construction Strategy towards Thermally Stable Thiepine Derivatives

S-fused heterocycles have become popular building blocks to construct functional polycyclic compounds.In contrast to the abundant synthetic methodologies for thiophene-fused aromatics,the synthesis of S-heterocycles containing six-membered thiopyran and seven-membered thiepine rings is much less reported owing to their unfavorable synthetic protocols and the thermal instabilities.Herein,a series of thiepine-containing polycyclic S-heterocycles have been successfully synthesized via different synthetic routes which involve initial construction of sulfur bridges and final ring-closure reactions.Therefore,the dilithium intermediates are ex-cluded,which facilitates the fusion on the thiepine ring with different S-heterocycles,including thiophene and thiopyran derivatives.Typically,a S-fused multi-membered polycyclic compound simultaneously involving thiophen,thiopyran,and thiepine rings has been successfully prepared.Interestingly,nucleus-independent chemical shift calculations reveal that the incorporated thiopyran and thiepine rings demonstrate aromatic and nonaromatic characteristics,respectively.Moreover,the thermal stabilities of the thiepine derivatives have been tremendously improved after the fusion on the three vinyl groups in the thiepine unit,which is attributed to the enhancements of the activation energies for the S-extrusion reactions,as revealed by density functional theory calculations.Therefore,our findings not only provide a facile synthetic methodology for S-fused multi-membered polycyclic heterocycles,but also furnish a novel construction strategy towards thermally stable thiepine derivatives.

New Core-Expanded Naphthalene Diimides for n-Channel Organic Thin Film Transistors

Four classes of core-expanded naphthalene diimides （la, lb, 2a, 2b, 3 and 4） that bear different elec- tron-deficient sulfur heterocycles were designed and synthesized. The solution-processed thin films of la, 2a, 3 and 4 operated well in air as n-channel organic transistors with electron mobility ranging from MO 6 to 0.14 cm2/Vs, depending on the different conjugated backbones. The thin film microstructure studies were also carried out to un- derstand the variations of the electron mobility for thin films of la, 2a, 3 and 4.