Uranyl photocatalysis: precisely controlled oxidation of sulfides with ground-state oxygen

正Sulfur-containing organic compounds such as sulfides,sulfoxides and sulfones, have played significant roles in the fields of organic synthesis, pharmaceuticals, and agrochemicals. The selective oxidation of the parent sulfides has been considered as one of the most straightforward methods for the construction of sulfoxides and sulfones. Therefore, a plethora of oxidative systems have been developed for the     

Solvent-free Synthesis of Dihydrofuran-fused [60]Fullerene Derivatives by High-speed Vibration Milling

Solvent-free organic reactions have been attracting great interest of chemists due to the elimination of the usage of harmful organic solvents,low costs,and simplicity in the procedure1.Solvent-free mechanochemical reactions of fullerenes were explored and are significant for the reactions of fullerenes because the low solubility of fullerenes in common organic solvents requires large quantity of organic solvents and some novel fullerene reactions could only occur in the solid-state reaction2.…     

Recent advances of dithienobenzodithiophene-based organic semiconductors for organic electronics

In recent years, fused aromatic dithienobenzodithiophene(DTBDT)-based functional semiconductors have been potential candidates for organic electronics. Due to the favorable features of excellent planarity, strong crystallinity, high mobility, and so on, DTBDT-based semiconductors have demonstrated remarkable performance in organic electronic devices, such as organic feld-effect transistor(OFET), organic photovoltaic(OPV), organic photodetectors(OPDs). Driven by this success, recent developments in the area of DTBDT-based semiconductors for applications in electronic devices are reviewed, focusing on OFET, OPV, perovskite solar cells(PSCs), and other organic electronic devices with a discussion of the relationship between molecular structure and device performance. Finally, the remaining challenges, and the key research direction in the near future are proposed, which provide a useful guidance for the design of DTBDT-based materials.     

Open-Shell Oligomers and Polymers:Theory,Characterization Methods,Molecular Design,and Applications

Open-shell oligomers and polymers have exhibited intriguing electronic and magnetic properties, making them highly desirable for a wide range of applications, including ambipolar organic field-effect transistors(OFETs), photodetectors, organic thermoelectrics, and spintronics.Although open-shell ground states have been observed in certain small molecules and doped organic semiconductors, the exploration of openshell ground-state conjugated polymers is still limited, and the strategies for design...     

Theoretical Studies on Electronic Spectra and Second-order Nonlinear Optical Properties of Barbituric Acid Derivatives Substituted with Schiff Base

Barbituric acid (BA) is a very important kind of compound in biological chemistry and medicine. It can be applied in abirritative medicine and antioxidants.1 It is an important sort of raw material for organic synthe-sis.2 It predicts the important reactive mechanism for organic synthesis.3 Some investigations for NLO prop-erties of a series of BA derivatives have been reported by Feng and coworkers in the view of theory.4,5 The Schiff base has extensive application in the fields of organi…     

Nanostructured strategies towards boosting organic lithium-ion batteries

Pursuing material development for next-generation batteries,organic electrode materials have shown great potential for lithium-ion batteries.However,their widespread adopting is plagued by intrinsic problems such as poor electronic conductivity,high dissolution inside electrolytes and unstable chemical peculiarity.Recently,nanostructured-strategies promoted organic electrodes with exotic properties for enhancing electron and ion transport together with the stability during electrochemical process,have received increasing attention and have been extensive applied in boosting the organic lithium-ion based energy storage.In this review,we summarize the applications of nanostructures to improve the performance of both organic anodes and cathodes,including(i)nanoscale design of zero-dimensional organic electrode materials,(ii)strategies of one-dimensional nanostructured organic electrode materials,(iii)construction of two-dimensional nanosized organic composite electrodes,and(iv)three-dimensional exploration of nanosized organic electrodes.We hope to stimulate high-quality applied research on understanding and handling the relationship between the nanostructure and performance of organic lithium-ion batteries that might speed up the commercialization of organic lithium ion batteries.     

Synthesis and Isolation of Diastereomers of Optically Active Cyclomercurated Ferrocenylimines

IntroductionOrganomercurials have been used extensively in organic synthesis and synthesis of other organometallics due to their ability to accommodate practically all the important organic functional groups and their ease in undergoing transmetallation for syntheses of transition metal organometallics which are very useful in organic synthesis. Recently, we reported the synthesis of optically active 1,2-disubstituted cyclomercurated ferrocenylimines by transmetallation reaction of planar chir…     

A Brief Introduction to Organic Electrodeposition and a Review of the Fabrication of OLEDs based on Electrodeposition Technology

Electrodeposition is an old and effective method for the fabrication of organic films. Though electrodeposited organic films have been widely used in various applications, highly luminescent films have been a great challenge because the electrochemically doped state may strongly quench the fluorescence. In the first part of this review, the organic electrodeposition techniques, along with general electropolymerization and other special electrodepositions are introduced. In the second part of the...     

Enhancement of intramolecular excimer formation and photodimerization of anthrylmethyl α,ω-alkanedioates via hydrophobic interactions

The fluorescence spectra and photodimerization of anthrylmethyl a,w-alkanedioates (A-Mn-A) both in organic and in aqueous organic mixed solvents have been studied.In aqueous organic mixed solvents strong intramolecular excimer emission is detected and the quantum yield for the intramolecular photodimerization is significantly greater than those in organic solvents.These observations suggest that hydrophobic interactions force A-Mn-A molecule to self-coil.The ratio of the head-to-head to head-to-tail products in the intramolecular photodimers of A-Mn-A depends on the length of the linking chain.This work presents a successful example of application of hydrophobic interactions to enhancement of large-ring formation.     

HYPERSALINE ENVIRONMENTS AND GENERATION OF PETROLEUM

Not only the mudstones and carbonates deposited in hypersaline environments, but also evaporites can be source rocks of petroleum. They all have a peculiar composition of hydrocarbon such as the strong predominance of phytane, the richness in gammacerane, the frequent preference of even carbon number n-alkanes, and have a generative potential for less mature oils in diagenesis of organic matter.     

6,6′‐Dimethoxygossypolone

6,6′‐Dimethoxygossypolone (systematic name: 7,7′‐dihydroxy‐5,5′‐diisopropyl‐6,6′‐dimethoxy‐3,3′‐dimethyl‐1,1′,4,4′‐tetraoxo‐2,2′‐binaphthalene‐8,8′‐dicarbaldehyde), C₃₂H₃₀O₁₀, is a dimeric molecule formed by oxidation of 6,6′‐dimethoxygossypol. When crystallized from acetone, 6,6′‐dimethoxygossypolone has monoclinic (P2₁/c) symmetry, and there are two molecules within the asymmetric unit. Of the four independent quinoid rings, three display flattened boat conformations and one displays a flattened chair/half‐chair conformation. The angles between the planes of the two bridged naphthoquinone structures are fairly acute, with values of about 68 and 69°. The structure has several intramolecular O—H...O and C—H...O hydrogen bonds and several weak intermolecular C—H...O hydrogen bonds, but no intermolecular O—H...O hydrogen bonds.     

Chlorido(dimethyl 2,2′‐bipyridine‐4,4′‐dicarboxylate‐κ2N,N′)(η5‐pentamethylcyclopentadienyl)rhodium(III) chloride 1‐hydroxypyrrolidine‐2,5‐dione disolvate

The title complex, [Rh(C₁₀H₁₅)Cl(C₁₄H₁₂N₂O₄)]Cl·2C₄H₅NO₃, has been synthesized by a substitution reaction of the precursor [bis(2,5‐dioxopyrrolidin‐1‐yl) 2,2′‐bipyridine‐4,4′‐dicarboxylate]chlorido(pentamethylcyclopentadienyl)rhodium(III) chloride with NaOCH₃. The Rh^III cation is located in an RhC₅N₂Cl eight‐coordinated environment. In the crystal, 1‐hydroxypyrrolidine‐2,5‐dione (NHS) solvent molecules form strong hydrogen bonds with the Cl⁻ counter‐anions in the lattice and weak hydrogen bonds with the pentamethylcyclopentadienyl (Cp*) ligands. Hydrogen bonding between the Cp* ligands, the NHS solvent molecules and the Cl⁻ counter‐anions form links in a V‐shaped chain of Rh^III complex cations along the c axis. Weak hydrogen bonds between the dimethyl 2,2′‐bipyridine‐4,4′‐dicarboxylate ligands and the Cl⁻ counter‐anions connect the components into a supramolecular three‐dimensional network. The synthetic route to the dimethyl 2,2′‐bipyridine‐4,4′‐dicarboxylate‐containing rhodium complex from the [bis(2,5‐dioxopyrrolidin‐1‐yl) 2,2′‐bipyridine‐4,4′‐dicarboxylate]rhodium(III) precursor may be applied to link Rh catalysts to the surface of electrodes.     

Hydrogen‐bonded layers in the 1:2 cocrystal of 2,2′‐dithiodibenzoic acid with isonicotinohydrazide

Cocrystallization of 2,2′‐dithiodibenzoic acid with isonicotinohydrazide from methanol solution yields the 1:2 cocrystal 2,2′‐dithiodibenzoic acid–isonicotinohydrazide (1/2), C₁₄H₁₀O₄S₂·2C₆H₇N₃O. The component molecules are linked by intermolecular O—H...N, N—H...O, N—H...N and C—H...O hydrogen bonds into layers running parallel to the (010) plane, and these layers are further linked into a three‐dimensional framework structure by means of weak aromatic π–π stacking interactions. As a potential cocrystallization agent, isonicotinohydrazide may be used for effective and versatile synthetic supramolecular strategies utilizing hydrogen bonding of specific molecular building blocks.     

Three anilides of 2,2′‐thiodibenzoic acid

The structures of N,N′‐bis(2‐methylphenyl)‐2,2′‐thiodibenzamide, C₂₈H₂₄N₂O₂S, (Ia), N,N′‐bis(2‐ethylphenyl)‐2,2′‐thiodibenzamide, C₃₀H₂₈N₂O₂S, (Ib), and N,N′‐bis(2‐bromophenyl)‐2,2′‐thiodibenzamide, C₂₆H₁₈Br₂N₂O₂S, (Ic), are compared with each other. For the 19 atoms of the consistent thiodibenzamide core, the r.m.s. deviations of the molecules in pairs are 0.29, 0.90 and 0.80 Å for (Ia)/(Ib), (Ia)/(Ic) and (Ib)/(Ic), respectively. The conformations of the central parts of molecules (Ia) and (Ib) are similar due to an intramolecular N—H...O hydrogen‐bonding interaction. The molecules of (Ia) are further linked into infinite chains along the c axis by intermolecular N—H...O interactions, whereas the molecules of (Ib) are linked into chains along b by an intermolecular N—H...π contact. The conformation of (Ic) is quite different from those of (Ia) and (Ib), since there is no intramolecular N—H...O hydrogen bond, but instead there is a possible intramolecular N—H...Br hydrogen bond. The molecules are linked into chains along c by intermolecular N—H...O hydrogen bonds.     

Dichloro(2,2′‐diamino‐4,4′‐bi‐1,3‐thiazole‐N3,N3′)copper(II)

The title complex, [CuCl₂(C₆H₆N₄S₂)], has a flattened tetrahedral coordination. The Cu^II atom is located on a twofold rotation axis and is coordinated by two N atoms from a chelating 2,2′‐di­amino‐4,4′‐bi‐1,3‐thia­zole ligand and by two Cl atoms. Intramolecular hydrogen bonding exists between the amino groups of the 2,2′‐di­amino‐4,4′‐bi‐1,3‐thia­zole ligand and the Cl atoms. The intermolecular separation of 3.425 (1) Å between parallel bi­thia­zole rings suggests there is a π–π interaction between them.     

Packing effects in 4,4′‐bis(4‐hydroxy­butyl)‐2,2′‐bi­pyridine and 4,4′‐bis(4‐bromo­butyl)‐2,2′‐bi­pyridine

Structure analyses of 4,4′‐bis(4‐hydroxy­butyl)‐2,2′‐bi­pyridine, C₁₈H₂₄N₂O₂, (I), and 4,4′‐bis(4‐bromo­butyl)‐2,2′‐bi­pyridine, C₁₈H₂₂Br₂N₂, (II), reveal intermolecular hydrogen bonding in both compounds. For (I), O—H·N intermolecular hydrogen bonding leads to the formation of an infinite two‐dimensional polymer, and π stacking interactions are also observed. For (II), C—H·N intermolecular hydrogen bonding leads to the formation of a zigzag polymer. The two compounds crystallize in different crystal systems, but both mol­ecules possess C_i symmetry, with one half mol­ecule in the asymmetric unit.     

Di‐μ‐chlorido‐bis[chlorido(4′‐p‐tolyl‐2,2′:6′,2′′‐terpyridine‐κ3N,N′,N′′)nickel(II)]: a supramolecular system constructed by C—H...Cl interactions

The title complex, [Ni₂Cl₄(C₂₂H₁₇N₃)₂], was synthesized solvothermally. The molecule is a centrosymmetric dimer with the unique Ni^II centre in a distorted octahedral N₃Cl₃ coordination environment. The chloride bridges are highly asymmetric. In the 4′‐p‐tolyl‐2,2′:6′,2′′‐terpyridine ligand, the p‐tolyl group is perfectly coplanar with the attached pyridine ring, and this differs from the situation found in previously reported compounds; however, there are no π–π interactions between the ligands. The terminal Cl atom forms four intermolecular C—H...Cl hydrogen bonds with one methyl and three methine groups. The methyl group also forms intermolecular C—H...π interactions with a pyridine ring. These nonclassical hydrogen bonds extend the molecule into a three‐dimensional network.     

基于2,4′-二羧基二苯甲酮构筑的具有一维梯状链和一维隧道的三维超分子体系

采用水热法设计合成了两个新型三维超分子化合物H₂L·H₂O (1)和[Ag(bpy)₂]·HL·H₂O (2) (其中bpy=2,2'-联吡啶, H₂L=2,4′-二羧基二苯甲酮),晶体结构分析表明,它们均是通过氢键采用不同的连接方式拓展而成。其中,化合物1 是2,4′-二羧基二苯甲酮和水分子通过O–H···O氢键形成的一维梯状链扩展构筑的三维超分子体系;化合物2 则是2,4′-二羧基二苯甲酮和水分子通过两种氢键形成含有一维隧道的三维超分子体系。有趣的是,[Ag(bpy)₂]⁺ 阳离子通过π–π 堆积和弱的Ag···Ag相互作用连在一起,进而以客体形式填充其中。荧光性质研究表明,由于存在bpy的螯合与堆积效应,化合物2相比配体和化合物1,其荧光发射峰发生红移。     

Bis[(dihydrogen pyrophosphato‐κ2O,O′)(2,2′:6′,2′′‐terpyridine‐κ3N,N′,N′′)copper(II)] 4.5‐hydrate

The title copper complex, [Cu(H₂P₂O₇)(C₁₅H₁₁N₃)]₂·4.5H₂O, consists of two very similar independent Cu(Tpy)H₂P₂O₇ monomeric units (Tpy is 2,2′:6′,2′′‐terpyridine) plus four and a half water molecules of hydration, some of which are disordered. Tpy units bind through the usual triple bite via their N atoms, and the H₂P₂O₇²⁻ anions coordinate through two O atoms from two different phosphate units. Each independent CuN₃O₂ chromophore can be described as a slightly deformed square pyramid, with one of them having a sixth, semicoordinated, O atom from a centrosymmetrically related CuN₃O₂ unit in a weakly bound second apical position suggesting an octahedral environment for the cation and weak dimerization of the molecule. The two independent complex molecules are connected via two strong O—H...O interactions between the phosphate groups to form hydrogen‐bonded dinuclear units, further linked into [111] columns, resulting in a very complex three‐dimensional supramolecular structure through a variety of classical and nonclassical hydrogen bonds, as well as π–π interactions.     

Tetraaqua(4,4′‐dimethyl‐2,2′‐bipyridine‐κ2N,N′)nickel(II) sulfate monohydrate: a simple molecule with an extremely complex hydrogen‐bonding scheme

The title ionic compound, [Ni(C₁₂H₁₂N₂)(H₂O)₄]SO₄·H₂O, is composed of an Ni^II cation coordinated by a chelating 4,4′‐dimethyl‐2,2′‐bipyridine ligand via its two N atoms [mean Ni—N = 2.056 (2) Å] and by four aqua ligands [mean Ni—O = 2.073 (9) Å], the net charge being balanced by an external sulfate anion. The whole structure is stabilized by a solvent water molecule. Even though the individual constituents are rather featureless, they generate an extremely complex supramolecular structure consisting of a central hydrogen‐bonded two‐dimensional hydrophilic nucleus made up of complex cations, sulfate anions and coordinated and solvent water molecules, with pendant hydrophobic 4,4′‐dimethyl‐2,2′‐bipyridine ligands which interact laterally with their neighbours viaπ–π interactions. The structure is compared with closely related analogues in the literature.