A-DA′D-A non-fullerene acceptors for high-performance organic solar cells

Since the world-record power conversion efficiency of 15.7% was achieved for organic solar cells(OSCs) in 2019, the newly developed non-fullerene acceptor(NFA) Y6 with an A-DA′D-A structure(A denotes an electron-accepting moiety, D denotes an electron-donating moiety) has attracted increasing attention. Subsequently, many new A-DA′D-A NFAs have been designed and synthesized, and the A-DA′D-A NFAs have played a significant role in the development of high-performance non-fullerene organic solar cells(NF-OSCs). Compared with the classical A-D-A-type acceptors, A-DA′D-A NFAs contain an electrondeficient core(such as benzothiadiazole(BT), benzotriazole(BTA), quinoxaline(Qx), or their derivatives) in the ladder-type fused rings to fine-tune the energy levels, broaden light absorption and achieve higher electron mobility of the NFAs. This review emphasizes the recent progress on these emerging A-DA′D-A(including Y-series) NFAs. The synthetic methods of DA′D-fused rings are introduced. The relationships between the chemical structure of the A-DA′D-A NFAs and the photovoltaic performance of the corresponding OSCs are summarized and discussed. Finally, issues and prospects for further improving photovoltaic performance of the OSCs are also proposed.     

Hydrothermal and Solvothermal Synthesis of the Complex Fluoride α′-SrAIF5

The complex fluoride α′-SrAlF5 has been synthesized through hydrothermal and solvothermal methods under mild conditions.The effects of the molar ratio of starting materials,temperature,reaction time and solvents on the synthesis of α′-SrAlF5 were discussed.The final products were characterized by XRD and SEM.The rod-like shape of α′-SrAlF5 is shown in SEM images.     

Theoretical study on the hydrolysis mechanism of N,N-dimethyl-N′-(2′,3′-dideoxy-3′-thiacytidine)formamidine

The hydrolysis mechanisms of N,N-dimethyl-N′-(2′,3′-dideoxy-3′-thiacytidine)formamidine (FA-3TC) in the gas phase and in aqueous solution were studied by use of the density functional theory B3LYP/6-31 G(d, p) method. Two possible reaction pathways in the title reaction were considered. In one pathway water attacks the C=N double bond first (path A) while in the other water attacks the C—N single bond first (path B). The calculated results indicate that the first step in both pathways is the rate-limiting process and path A is more favorable than path B in the gas phase. The effect of solvent water on the title reaction was assessed at the B3LYP/6-31 G(d, p) level of theory based on the po-larizable continuum model (CPCM). In water the first mechanism (path A) is also favored.     

Synthesis,Crystal Structure and Spectroscopic Properties of N,N′-Diphenyl-N,N′-bis(2-fluorophenyl)-1,1′-biphenyl-4,4′-diamine

A fluorinated tetraphenylbenzidine derivative, N,N′-diphenyl-N,N′-bis(2-fluorophenyl)-1,1′-biphenyl-4,4′-diamine (C36H26F2N2, Mr = 524.59) was synthesized via the palladiumcatalyzed Buchwald-Hartwig reaction of N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine with 2-fluoroiodobenzene (yield: 75%) and structurally characterized. It crystallizes in monoclinic, space group P21/n with a = 9.820(7), b = 14.305(11), c = 10.233(8) , β = 108.973(9)o, V = 1359.3(18) 3, Z = 2, Dc = 1.282 g/cm3, μ(MoKα) = 0.084 mm-1, F(000) = 548, S = 1.018, the final R = 0.0439 and wR = 0.0928. It presents a linear centrosymmetric framework constituted by a linkage of biphenyl as a bridge and two fluorinated diphenylamine moieties. The UV-Vis absorption and fluorescence spectra of the title compound were also investigated. This compound emits intense blue fluorescence with a peak wavelength of 406 nm in film.     

Crystal Structure of (R)-3,3′-Bis(benzyloxymethyl)-1,1′-bi-2,2′-naphthol and Its Applications in Enantioselective Lewis Acid Catalyzed Addition of Diethylzinc to Aldehydes

The title compound (R)-3,3′-bis(benzyloxymethyl)-1,1′-bi-2,2′-naphthol (R)-3 has been synthesized through the deprotection of MOM group by iPrOH/HCl in 83% isolated yield and the suitable single crystals for X-ray diffraction were obtained by recrystallization at room temperature from the mixture solvents. Crystallographic data for (R)-3: C36H30O4, Mr = 526.60, triclinic, space group P1, a = 10.057(6), b = 11.934(7), c = 12.314(6) , α = 85.52(2), β = 70.245(13), γ = 76.554(11)o, Z = 2, V = 1352.8(13)3, Dc = 1.293 g/cm3, F(000) = 556, R = 0.0745, wR = 0.1933 and μ(MoKα) = 0.083 mm-1. The title compound (R)-3 was found to be effective in the enantioselective addition of diethylzinc to aldehydes both in the presence and absence of Ti(OiPr)4. In the latter case, (R)-3 showed much higher catalytic activity and enantioselectivity than (R)-BINOL′s.     

Microwave promoted one-pot synthesis of 3-(2′-amino-3′-cyano-4′-arylpyrid-6′-yl)coumarins

A facile procedure for the synthesis of 3-(2′-amino-3′-cyano-4′-arylpyrid-6′-yl)coumarins are being reported starting from 3- acetylcoumarin,aromatic aldehydes and malononitrile.The reactions were carded out on microwave irradiation in good yield with short time and easy work-up.The structures of all the compounds have been confirmed on the basis of their analytical,IR,~1H NMR, and mass spectral data.     

Conformation preference and related intramolecular noncovalent interaction of selected short chain chlorinated paraffins

Short chain chlorinated paraffins(SCCPs) are not only research focus of environmental issues but also interesting model molecules for organic chemistry which exhibit diverse conformation preference and intramolecular noncovalent interactions(NCIs). A systematic study was conducted to reveal the conformation preference and the related intramolecular NCIs in two C_(10)-isomers of SCCPs, 5,5,6,6-tetrachlorodecane and 4,4,6,6-tetrachlorodecane. The overall conformation profile was determined on the basis of relative energies calculated at the MP2/6-311++G(d,p) level with the geometries optimized by B3LYP/6-311++G(d,p) method. Then, quantum theory of atoms in molecules(QTAIM) has been adopted to identify the NCIs in the selected conformers of the model molecules at both B3LYP/6-311++G(d,p) and M06-2X/aug-cc-pvdz level. Different chlorine substitution modes result in varied conformation preference. No obvious gauche effect can be observed for the SCCPs with chlorination on adjacent carbon atoms. The most stable conformer of 5,5,6,6-tetrachlorodecane(t Tt) has its three dihedral angles in the T configuration, and there is no intramolecular NCIs found in this molecule. On the contrary, the chlorination on interval carbon atoms favors the adoption of gauche configuration for the H–C–C–Cl axis. Not only intramolecular H···Cl contacts but also H···H interactions have been identified as driving forces to compensate the instability from steric crowding of the gauche configuration. The gggg and g′g′g′g′ conformers are the most popular ones, while the populations of tggg and tg′g′g′ conformer are second to those of the gggg and g′g′g′g′ conformers. Meanwhile, the M06-2X method with large basis sets is preferred for identification of subtle intramolecular NCIs in large molecules like SCCPs.     

{[Co(4，4′-bipy)(ambdc)(H2O)2](4，4′-bipy)(DMF)}n合成与晶体结构

A novel coordination polymer of {[Co(4,4′-bipy)(ambdc)(H₂O)₂](4,4′-bipy)(DMF)}_n has been synthesized using 5-aminoisophthalic acid (H₂ambdc), 4,4′-bipyridine(4,4′-bipy) and metal salts. The ambdc ligand in title compound has a μ₂-monodentate coordination mode and the structure of the title compound is a two-dimensional network. CCDC: 279054.     

SYNTHESIS OF POLYBINAPHTHYLS INCORPORATING CHIRAL (R)-1,1′-BI-2,2′-NAPHTHOL ENTITIES WITHp-DIVINYLBENZENE BY Pd-CATALYZED HECK REACTION

Polymer (Ⅰ) and polymer (Ⅱ) were obtained by the polymerization of (R)-6,6′-dibromo-2,2′-binaphtho-20-crown-6(M-1) and (R)-6,6′-dibromo-2,2′-di(methoxyethoxymethyloxy)-1,1′-binaphthyl (M-2) with p-divinylbenzene under Pdcatalyzed Heck reaction. The UV, fluorescence and CD spectra of polymer (Ⅰ) and (Ⅱ) are similar due to the same linkers present in their polymer chain. Polymers (Ⅰ) and (Ⅱ) can emit strong blue fluorescence and are expected to have potential applications in polarized blue-light emitting sensors. The chiral conjugated polymers (Ⅰ) and (Ⅱ) exhibit a strong Cotton effect in their circular dichroism (CD) spectra, indicating a high rigidity of polymer backbone.     

SYNTHESIS OF POLYBINAPHTHYLS INCORPORATING CHIRAL （R）-1,1′-BI-2,2′-NAPHTHOL ENTITIES WITH p-DIVINYLBENZENE BY Pd-CATALYZED HECK REACTION

Polymer (Ⅰ) and polymer (Ⅱ) were obtained by the polymerization of (R)-6,6′-dibromo-2,2′-binaphtho-20-crown-6 (M-l) and (R)-6,6′-dibromo-2,2′-di(methoxyethoxymethyloxy)-1,1′-binaphthyl (M-2) with p-divinylbenzene under Pdcatalyzed Heck reaction. The UV, fluorescence and CD spectra of polymer (Ⅰ) and (Ⅱ) are similar due to the same linkers present in their polymer chain. Polymers (Ⅰ) and (Ⅱ) can emit strong blue fluorescence and are expected to have potential applications in polarized blue-light emitting sensors. The chiral conjugated polymers (Ⅰ) and (Ⅱ) exhibit a strong Cotton effect in their circular dichroism (CD) spectra, indicating a high rigidity of polymer backbone.     

Syntheses, Characterization and Crystal Structures of Two-dimensional 4,4′-Bipyridyl Lead Halides, PbI_2(4,4′-bpy) and PbBr_2(4,4′-bpy)

IntroductionLinear bidentate N,N′- donor complexes havebeen extensively used in recent years to obtain thepolymeric frameworks with potential applicationprospects in different areas of material sciences,such as electrical conductivity[1] ,magnetism[2 ] ,photomechanical behaviour[3 ] and catalysis[4～ 6] .Among them,4,4′- bipyridine( bpy) has beenproven to be able to form one- dimensional poly-mers[7] ,two- dimensional layers[4] ,and three- di-mensional frameworks exhibiting the interpene-tra…     

Enantioseparation of Racemic Anti-hepatitis New Drug Bicyclol with Crystallization

(±)-Bicyclol, 4, 4′-dimethoxy-2, 3, 2′, 3′-bis(methylenedioxy)-6-hydroxymethyl-6′- methoxy-carbonyl biphenyl is a new anti-hepatitis drug. The clinical study showed that bicyclol is a promising drug for chronic viral hepatitis B and C and it can markedly improve the clinical symptoms, such as elevated ALT (alanine aminotransferase) and AST (aspartate aminotransferase) in serum, and also in part of patients it returned positive HBeAg and HBV-DNA to negative. Bicyclol has been approve…     

Highly Soluble Phenylethynyl-terminated Imide Oligomers and Thermosetting Polyimides Based on 2,2′3,3′-Biphenyltetracarboxylic Dianhydride

The properties of a series of imide oligomers were characterized according to their molecular weights, solubility, and thermal and rheological properties. This series of imide oligomers was synthesized via a two-step method using 2,2′,3,3′-biphenyltetracarboxylic dianhydride(3,3′-BPDA) and aromatic diamines as the monomers, and 4-phenylethynyl phtlialic anhydride(PEPA) as the end-capping agent. The imide oligomers based on 3,3′-BPDA showed excellent solubility in low boiling point solvents and low melt viscosity, which were attributed to their unique bent architectures. High-performance thermosetting polyimides were produced from these oligomers via thermal crosslinking of the phenylethynyl groups. The mechanical and thermal properties of the thermosets were studied using tensile testing, dynamic mechanical thermal analysis(DMTA), and thermogravimetric analysis(TGA). The 3,3′EPDA-based thermosets exhibited excellent thermal properties, with glass transition temperatures of up to 455℃, and 5% mass loss temperatures of up to 569℃ in air. The thermosets based on 3,3-BPDA showed superior thermal properties compared to those derived from TriA-X series oligomers.     

1，4-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)丁二酮-(1，4)合双铜(Ⅱ)配合物的合成、表征、非等温热分解反应动力学及电化学性质

The paper reported the synthetic procedure and character of Copper(Ⅱ) binuclear coordination compound of 1,4-bis-(1′-phenyl-3′-methyl-5′-pyrazolone-4′)-1,4-butanedione. The non-isothermal kinetic of the thermal decomposition of the complex has been studied from the TG-DTG curves by means of the Achar et al and Coats-Redfern methods. The electrochemical characterization of the complex were studied by means of powder microelectrodes technique.     

Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of the Complex Cu(o-Methylbenzoic acid)_2(2,2′-bipy)·(H_2O)

The title complex (C26H24CuN2O5, Mr = 508.01) has been synthesized by o-me- thylbenzoic acid, 2,2′-bipyridine (bipy) and copper perchlorate in the mixed solvent of water and methanol. It crystallizes in orthorhombic, space group P212121 with a = 0.70814(10), b = 1.6953(3), c = 1.9539(3) nm, V = 2.3457(6) nm3, Dc = 1.439 g/cm3, Z = 4, μ = 0.971 mm-1, F(000) = 1052, R = 0.0432 and wR = 0.0860. The structural determination shows that the copper atom is coordinated by three oxygen atoms from two o-methylbenzoic acids and one water molecule together with two nitrogen atoms from 2,2′-bipyridine, giving a distorted square-pyramidal coordination geometry. The cyclic voltammetric behavior of the complex is also discussed.     

Thin-layer Spectroelectrochemistry of 3,3′,5,5′-Tetramethyl-benzidine on Pt Minigrid Optically Transparent Electrode

3,3′,5,5′-Tetramethylbenzidine(TMB)-H2O2-horseradish peroxidase(HRP) voltammetric enzyme linked immunoassay system1 has very high sensitivity, low detection limit and wide detection range for the determination of some plant viruses. However, the understanding of the mechanism of HRP catalyzed by H2O2 oxidizing TMB in this system is of significance. In the previous paper, we have reported the spectroelectro- chemical study of TMB on SnO2: F film optically transparent electrode in the …     

Fe_3O_4@MCM-48-OSO_3H磁性核壳纳米粒子催化3,3′-双吲哚高效合成(英文)

Magnetite nanoparticles coated with sulfuric acid-functionalized mesoporous MCM-48 were synthesized and used as a catalyst in three-component domino reactions of indoles, arylglyoxal monohydrates and N-arylenaminones to furnish the desired 3,3′-bisindoles by formation of two C–C and one C–N bonds in a smooth cascade with good yields under mild reaction conditions. The catalyst was recovered easily and maintained activity in successive runs.     

Synthesis,Crystal Structure and Magnetic Properties of a Co(Ⅱ) Complex Containing 2′-(l′-Methyl)benzimidazolyl-substituted Nitronyl Nitroxide

A new complex [Co(NIT-1′-MeBzIm)2Cl2](NIT-1′-MeBzIm = 2-{2′-[(l′-methyl)-benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been prepared and structurally characterized by X-ray diffraction method.The complex crystallizes in the monoclinic system,space group C2/c,Z = 4.Crystal data:C30H38Cl2CoN8O4,Mr = 704.51,a = 17.074(3),b = 21.350(3),c = 11.6962(19),β = 108.879(2)°,V = 4034.3(11)3,Dc = 1.160 g/cm3,μ(MoKα) = 0.597 mm-1,F(000) = 1468,R = 0.0422 and wR = 0.1141 for 2577 observed reflections with I > 2σ(I).X-ray analysis reveals that the Co(Ⅱ) ion is six-coordinated with a distorted octahedral geometry.Temperature dependence of susceptibility measurements shows the existence of antiferromagnetic interactions between the Co(Ⅱ) ion and the radicals(J =-52.88 cm-1).     

Approach to 2′-(Dialkylamino)-1-alkyl-4′H-spiro[indoline-3,5′-oxazole]-2,4′-diones and 1,3-Oxazin-4-ones via Cyclization of Vilsmeier Salts withα-Hydroxy andβ-Carbonyl Amides

A straiglitforward and efficient synthetic method of 2′-(dialkylammo)-l-alkyl-4′H-spiro[indoline-3,5′-oxazole]-2,4′-diones and 2-(dialkylamino)-5,6-dihydro-4H-naphtho[2,1-e][1,3]oxazin-4-one-derivatives have been developed from a-hydroxy andβ-carbonyl amides and various Vilsmeier salts.A wide range of heterocyclic compounds were obtained in excellent yields(up to 97%),which will provide promising candidates lor chemical biology and drug discovery.     

手性苯并咪唑铜(Ⅱ)络合物催化合成1,1''''-联-2萘酚

In the past several decades, much attention has been paid to optically active, C2-asymmetric 1,1′-binaphthalene-2,2′-diol and its derivatives because of their application in inducing chirality in asymmetric synthesis[1,2]. Enantiomerically pure 1,1′-binaphthalene-2,2′-diol has been prepared by many methods ranging from the classical resolution via crystallization of the diastereoisomeric salts[3] to asymmetric oxidative coupling[4～6].