氧族元素间共价单键参与的无机反应机理

结合一些热力学数据和动力学过程,运用亲电和亲核的概念,初步阐释了一些O―O键、S―S键参与的氧化还原反应的机理,并利用Gaussian09程序的计算对一些已有的机理和猜想进行了验证,以此说明无机反应机理的一些规律。

Hierarchical N-doped porous carbon hosts for stabilizing tellurium in promoting Al-Te batteries

Aluminum batteries are attractive in electrochemical energy storage due to high energy density and lowcost aluminum,while the energy density is limited for the lack of favorable positive electrode materials to match aluminum negative electrodes.Tellurium positive electrode is intrinsically electrically conductive among chalcogen and holds high theoretical specific capacity(1260.27 mAh g^(-1)) and discharge voltage plateau(~1,5 V).However,the chemical and electrochemical dissolution of Te active materials results in the low material utilization and poor cycling stability.To enhance the electrochemical performance,herein a nitrogen doped porous carbon(N-PC) is derived from zeolite imidazolate framework(ZIF-67)as an effective tellurium host to suppress the undesired shuttle effect.In order to inhibit the volume expansion of N-PC during the charge/discharge process,the reduced graphene oxide(rGO) nanosheets are introduced to form a stable host materials(N-PC-rGO) for stabilizing Te.The physical encapsulation and chemical confinement to soluble tellurium species are achieved.N-PC-rGO-Te positive electrode exhibits an improved initial specific capacity and long-term cycling performance at a current density of 500 mA g^(-1)(initial specific capacity:935.5 mAh g^(-1);after 150 cycles:467.5 mAh g^(-1)), highlighting a promising design strategy for inhibiting chemical and electrochemical dissolution of Te.

Methane oxidative carbonylation catalyzed by rhodium chalcogen halides over carbon supports

Gas phase carbonylation of methane is studied in the presence of molecular oxygen over pure carbon carriers and carbon supported rhodium chalcogen halides. Activated carbons and fullerene blacks have been used as carbon supports. XPS and IR-spectroscopy data show the formation of rhodium chalcogen halides in solids prepared by different methods. We have found that the productivity of acetic acid by carbon supported rhodium chalcogen halides depends strongly on the carbon carrier and the method of the catalyst preparation. Namely, the catalyst with highest productivity for the acetic acid is prepared by synthesizing the rhodium chalcogen halide over the carbon support followed by thermal destruction. We have also found that rhodium chalcogen halides over activated carbons are more active compared with fullerene supported catalysts.

Physical properties of ternary thallium chalcogenes Tl2MQ3（M = Zr, Hf; Q = S, Se, Te） via ab-initio calculations

We have reported a first principles study of structural, mechanical, electronic, and thermoelectric properties of the monoclinic ternary thallium chalcogenes Tl2MQ3(M = Zr, Hf;Q = S, Se, Te). The electronic band structure calculations confirm that all compounds exhibit semiconductor character. Especially, Tl2ZrTe3 and Tl2HfTe3 can be good candidates for thermoelectric materials, having narrow band gaps of 0.169 eV and 0.21 eV, respectively. All of the compounds are soft and brittle according to the second-order elastic constant calculations. Low Debye temperatures also support the softness. We have obtained the transport properties of the compounds by using rigid band and constant relaxation time approximations in the context of Boltzmann transport theory. The results show that the compounds could be considered for room temperature thermoelectric applications(ZT ~ 0.9).

Catalytic perfomance of rhodium chalcogen halides and rhodium chalcogenides over silica supports in methane oxidative carbonylation

The gas phase methane oxidative carbonylation was studied in the presence of molecular oxygen over silica materials including their mechanical mixtures with rhodium chalcogen chlorides obtained in non-aqueous inorganic media. The formation of Rh4SCl7, Rh4S9Cl2, Rh4SesCl3 and Rh3Se3Cl solids was confirmed by elemental analysis, IR absorption spectroscopy, XPS and X-ray diffraction. Silica, vanadium-, and molybdenum-containing mesoporous molecular sieves have been used as supports. It was found that productivity of oxygenates （methanol, methyl acetate and acetic acid） depends mainly on the method of the catalyst preparation and the type of the support.

Electron—rich Polynuclear Transition Metal Clusters：I.The Clusters wit

This paper presents a versatile method for synthesizing electron-rich polynuclear transition metal clusters with chalcogen bridges and phosphine ligands.The reactions of transition metal complexes(R3P)2MX2(M=Co,Ni;R=Ph,Bu,Et;X=Cl,Br) with bridging reagents Na2Ex (E=S,Se;x=1.2) are described.The geometric and electronic structures of a series of polynuclear transition metal clusters with trianglar M3 units are also discussed.

Chalcogen Bonds in Small-Organic Molecule Compounds Derived from the Cambridge Structural Database (CSD)

Growing interest in non-covalent interactions involving chalcogen atoms has been ascribed to their importance in crystal engineering, molecular recognition and macromolecular edifices. The present study is dealing with chalcogen bonds involving divalent Sulphur, Selenium and Tellurium atoms, acting as sigma-hole donors, in small-molecule compounds using the Cambridge Structural Database (CSD) in conjunction with ab initio calculations. Results derived from CSD surveys and computational study revealed that nucleophiles formed complexes with the chalcogen-bond donors R1-X-R2 (X = S, Se or Te). The main forces stabilizing the complexes were chalcogen bonds, enhanced by dispersion interactions. Complexation pattern and energetics show that nucleophile bonding at divalent S, Se and Te atoms is a relatively strong and directed interaction. The bond consists of a charge transfer from a nucleophile atom lone pair to an X-R1 or X-R2 antibonding orbital.

Perturbation of autophagy pathways in murine alveolar macrophage by 2D TMDCs is chalcogen-dependent

Increasing risks of incidental and occupational exposures to two-dimensional transition metal dichalcogenides(2D TMDCs)due to their broad application in various areas raised their public health concerns.While the composition-dependent cytotoxicity of 2D TMDCs has been well-recognized,how the outer chalcogenide atoms and inner transition metal atoms differentially contribute to their perturbation on cell homeostasis at non-lethal doses remains to be identified.In the present work,we compared the autophagy induction and related mechanisms in response to WS_(2),NbS_(2),WSe_(2)and Nb Se_(2)nanosheets exposures in MH-S murine alveolar macrophages.All these 2D TMDCs had comparable physicochemical properties,overall cytotoxicity and capability in triggering autophagy in MH-S cells,but showed outer chalcogen-dependent subcellular localization and activation of autophagy pathways.Specifically,WS_(2)and NbS_(2)nanosheets adhered on the cell surface and internalized in the lysosomes,and triggered m TOR-dependent activation of autophagy.Meanwhile,WSe_(2)and Nb Se_(2)nanosheets had extensive distribution in cytoplasm of MH-S cells and induced autophagy in an m TOR-independent manner.Furthermore,the 2D TMDCs-induced perturbation on autophagy aggravated the cytotoxicity of respirable benzo[a]pyrene.These findings provide a deeper insight into the potential health risk of environmental 2D TMDCs from the perspective of homeostasis perturbation.

Synthesis and applications of thiosulfonates and selenosulfonates as free-radical reagents

Chalcogenative sulfones(thiosulfonates and selenosulfonates), as reactants for organic transformations,are widely used and interesting because of their potential to react with nucleophiles, electrophiles, and free radicals. As stable radical reagents, the synthesis and applications of chalcogenative sulfones have opened up a novel pathway to synthesize many kinds of compounds containing sulfur or selenium motifs. However, despite the numerous recent works on the synthesis and applications of thiosulfonates and selenosulfonates as radical reagents, no review has yet provided a summary of the literature. In this paper, we aim to review the synthesis and applications strategies of chalcogenative sulfones as radical reagents reported over the past several decades. Different types of catalysis are discussed in this review:(i) metal catalysis;(ii) visible-light catalysis;(iii) synergistic catalysis;and(iiii) other types. Concurrently,in visible-light catalysis and metallaphotoredox catalysis sections, we highlight that developing relatively environmentally friendly synthetic methods in this area is always a great challenge, but also a persistent pursuit. Finally, the scopes, limitations, mechanisms, and existing problems of some reactions are described briefly.

Chalcogen Effect of Atom Substitution on the Properties of Tris(2,4,6-trichlorophenyl)methyl(TTM)Radical

Luminescent open-shell organic radicals have recently been regarded as one of the most potential materials in organic light-emitting diodes(OLEDs).Herein,we have synthesized two new organic radicals,namely tris{4-[4-(tert-butyl)phenoxy]-2,6-dichlorophenyl}methane radical(TTM-O)and tris(4-{[4-(tert-butyl)-phenyl]thio}-2,6-dichlorophenyl)methane radical(TTM-S),by the substitution of chalcogen atom elements at the para position of conventional tris(2,4,6-trichlorophenyl)methyl(TTM)radical moiety.Interestingly,both TTM-O and TTM-S exhibited significantly enhanced photostability compared with the unsubstituted TTM radical parent.Moreover,the chalcogen atom also had a crucial impact on the photoluminescence quantum yield(PLQY)of the radicals,i.e.,the PLQY of TTM-S was greatly enhanced compared to TTM radical while TTM-O was nearly non-emissive.Particularly,TTM-S showed intense PLQY of 37.54%and 185-fold longer photostability than that in cyclohexane solution of TTM.

Organotellurium catalysis-enabled utilization of molecular oxygen as oxidant for oxidative deoximation reactions under solvent-free conditions

Catalyzed by commercially available(PhTe)2, molecular oxygen could be utilized as the mild, cheap and safe oxidant for oxidative deoximation reactions under solvent-free conditions. As the first report on organotellurium-catalyzed deoximation reaction, this work not only provides an efficient deoximation method, but also discloses new features of tellurium catalyst different from those of the organoselenium catalysts.

Chalcogen cathode and its conversion electrochemistry in rechargeable Li/Na batteries

Chalcogen elements,such as sulfur(S),selenium(Se),tellurium(Te)and the interchalcogen compounds,have been studied extensively as cathode materials for the next-generation rechargeable lithium/sodium(Li/Na)batteries.The high energy output of the Li/Na-chalcogen battery originates from the two-electron conversion reaction between chalcogen cathode and alkali metal anode,through which both electrodes are able to deliver high theoretical capacities.The reaction also leads to parasitic reactions that deteriorate the chemical environment in the battery,and different cathode-anode combinations show their own features.In this article,we intend to discuss the fundamental conversion electrochemistry between chalcogen elements and alkali metals and its potential influence,either positive or negative,on the performance of batteries.The strategies to improve the conversion electrochemistry of chalcogen cathode are also reviewed to offer insights into the reasonable design of rechargeable Li/Nachalcogen batteries.

Te-mediated electro-driven oxygen evolution reaction

In the 21^(st)century,the rapid development of human society has made people’s demand for green energy more and more urgent.The high-energy-density hydrogen energy obtained by fully splitting water is not only environmentally friendly,but also is expected to solve the problems caused by the intermittent nature of new energy.However,the slow kinetics and large overpotential of the oxygen evolution reaction(OER)limit its application.The introduction of Te element is expected to bring new breakthroughs.With the least electronegativity among the chalcogens,the Te element has many special properties,such as multivalent states,strong covalentity,and high electrical conductivity,which make it a promising candidate in electrocatalytic OER.In this review,we introduce the peculiarities of Te element,summarize Te doping and the extraordinary performance of its compounds in OER,with emphasis on the scientific mechanism behind Te element promoting the OER kinetic process.Finally,challenges and development prospects of the applications of Te element in OER are presented.

A highly active and selective chalcogen bond-mediated perchlorate channel

Artificial membrane transporters that either use chalcogen bonds to facilitate transmembrane flux of anions or show high selectivity toward perchlorate anions are rare.In this work,we report on one such novel monopeptide-based transporter system,featuring both chalcogen bonds for highly efficient anion transport and high transport selectivity toward ClO_(4)^(-) anions.Structurally,these monopeptide molecules associate with each other via H-bonds to produce H-bonded 1D stack that not only one dimensionally but also directionally aligns the terminal bicyclic thiophene motifs to the same side.Functionally,these well-aligned thiophenes create a sulfur-rich transmembrane pathway,combinatorially fine-tunable to enable anions to efficiently cross the membrane in the increasing activity of Cl^(-)<Br^(-)<NO_(3)^(-)<ClO_(4)^(-) via chalcogen bonds,with EC_(50)values of 0.75,0.40,0.37 and 0.093μmol/L(0.3 mol%relative to lipid molecules),respectively.

What Defines a Crystal Structure? Effects of Chalcogen Atoms in 3,7-Bis(methylchalcogeno)benzo[1,2-b:4,5-b′]dichalcogenophene-Based Organic Semiconductors

To understand the effects of chalcogen atoms on the crystal structure of the series of 3,7-bis(methylchalcogeno)benzo[1,2-b:4,5-b′]dichalcogenophene-based organic semiconductors,three benzodifuran derivatives(1—3)and dimethoxy derivatives of benzodithiophene and benzodiselenophene(4 and 7)were newly synthesized to complete the“3×3 matrix”of the oxygen-,sulfur-,and selenium-derivatives(1—9).The crystal structures of 1—9 were classified into four classes,sandwich pitchedπ-stack(1),dimeric(2 and 3),pitchedπ-stack(4,5,7,8,9),and brickwork structure(6 and 9).The causes for the different crystal structures depending on the chalcogen atoms were investigated by the theoretical calculations,indicating that the chalcogen atoms in the core and substituents primarily affected the packing structures.Although the crystal growth in the vapor phase afforded different polymorphs,the relationship between the crystal structure and the carrier transport property was carefully investigated.

Air Stable Chalcogen-Doped Rubicenes with Diradical Character

Air stable diradicaloid polycyclic aromatic hydrocarbon(PAH)materials possess unique electronic and magnetic properties for various applications.In general,long conjugated distances between two radical centers are required to improve the air stability,thereby complicating the synthetic procedures.Herein,the chalcogen containing rubicenes(O-,S-,and Se-rubicenes)were systematically investigated to understand the chalcogen effects on chalcogen-rubicene physicochemical properties.Impressively,these rubicenes presented unprecedented diradical characterwithin one simple benzene ring and excellent air stabilities.Theirdiradicalcharacterweremanifested by single-crystal X-ray studies,variable-temperature nuclear magnetic resonance,and electron spin resonance.Furthermore,the nucleus independent chemical shifts andthe anisotropy of the induced currentdensity calculations revealed that the formation of diradical was caused by a pro-aromaticity driving force.Importantly,the diradical character of rubicenes are visualizedbyFractionalOccupationNumberWeighted Electron Density(FOD)plots,which present high NFOD values from 1.651 to 1.830.This contribution provided distinctive insights into the structure and property relationship of PAH diradicals.