Syntheses and Crystal Structures of Four Cobalt Supramolecular Architectures with Hmtyaa Ligand

Four cobalt supramolecular architectures with Hmtyaa（2-（5-methyl-1,3,4-thiadiazol-2-ylthio）acetic acid） ligand have been synthesized.[Co（mtyaa）2（H2O）4]·4（H2O）（1）：triclinic,space group P1 with a = 6.7537（18）,b = 8.591（2）,c = 10.615（3） ,α = 96.495（4）,β = 99.955（5）,γ = 103.615（5）°,V = 581.9（3） 3,Z = 1,Mr = 581.52,Dc = 1.659 g/m3,μ = 1.158 mm-1,F（000） = 301,Rint = 0.0557,R = 0.0377 and wR = 0.1056 for 1854 observed reflections with Ⅰ 〉 2σ（Ⅰ）;{[Co（4,4＇-bipy）（H2O）4]·2（mtyaa）·2（H2O）}n（2）：triclinic,space group P1 with a = 7.669（2）,b = 8.840（3）,c = 11.521（4） ,α = 79.912（5）,β = 73.954（5）,γ = 86.612（6）°,V = 738.9（4） 3,Z = 1,Mr = 701.67,Dc = 1.577 g/m3,μ = 0.924 mm-1,F（000） = 363,Rint = 0.0636,R = 0.0498 and wR = 0.1311 for 2155 observed reflections with Ⅰ 〉 2σ（Ⅰ）;{[Co（4,4＇-bipy）（mtyaa）（H2O）3]（mtyaa）·2（H2O）}（3）：monoclinic,space group Pc with a = 7.7832（17）,b = 11.527（3）,c = 31.483（7） ,β = 91.952（4）°,V = 2822.9（11） 3,Z = 4,Mr = 683.65,Dc = 1.609 g/m3,μ = 0.963 mm-1,F（000） = 1412,Rint = 0.0758,R = 0.0609 and wR = 0.1095 for 5841 observed reflections with I 〉 2σ（I）;{[Co（bpe）（mtyaa）2（H2O）2]}n（4）：monoclinic,space group C2/c with a = 19.290（11）,b = 12.027（7）,c = 14.865（8） ,β = 125.648（8）°,V = 2802（3）3,Z = 4,Mr = 657.66,Dc = 1.559 g/m3,μ = 0.959 mm-1,F（000） = 1356,Rint = 0.0456,R = 0.0332 and wR = 0.0985 for 2299 observed reflections with Ⅰ 〉 2σ（Ⅰ）.

Syntheses,challenges and modifications of single-crystal cathodes for lithium-ion battery

Single-crystal cathodes(SCCs)are promising substitute materials for polycrystal cathodes(PCCs)in lithium-ion batteries(LIBs),because of their unique ordered structure,excellent cycling stability and high safety performance.Cathode materials with layered(LiCoO_(2),LiNi_xCo_yMnzO_(2),LiNi_xCo_yAl_(2)O_(2))and spinel structure(LiMn_(2)O_(4),LiNi_(0.5)Mn_(1.5)O_(4))show a relatively stable electrochemical performance,but still lack of sufficient attention in research field.In this review,we begin with the definition,structural features and electrochemical advantages of SCCs.Common SCCs synthesis methods and the thermodynamic growth mechanism of SCCs with oriented facet exposure are summarized in the following part.Then we introduce the problems and challenges of SCCs faced and the corresponding modification strategies.Finally,the industrialization progress of SCCs is brifly outlined.We intend to tease out the difficulties and advances of SCCs to provide insights for future development of high-performance SCCs for practical LIBs.

Syntheses,Structures,and Properties of Two New Coordination Polymers Based on Tetracarboxylate and 2,2′-Bipyridine Mixed Ligands

Two new coordination polymers {[Zn2L1（2,2＇-bpy）2（H2O）2]·4H2O}n（1） and [Zn2L2（2,2＇-bpy）2（H2O）2]n（2）（H4L1 = terphenyl-2,2＇,4,4＇-tetracarboxylic acid, H4L2 = quarterphenyl-2,2＇,4,4＇-tetracarboxylic acid, and 2,2＇-bpy = 2,2＇-bipyridine） have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction studies. Complex 1 displays 2D wavelike networks, which are further joined together through O–H···O hydrogen bonds to give a 3D supramolecular network. Complex 2 exhibits 1D ladder-like chains, and they are further joined together by π-π stacking and O–H···O hydrogen bonding interactions to form a 3D supramolecular network. The results indicate that the backbone of carboxylate ligands has significant effects on the formation and structure of the resulting functional coordination polymers. Additionally, thermal stability and photoluminescent properties of 1 and 2 are also investigated in detail.

Syntheses,Crystal Structures,DFT Calculation and Optical Properties of a Schiff Base and Its Dinuclear Mercury(Ⅱ)Complex

A pyridine-contained Schiff base ligand L（L =（pyridine-2-vinyl）hydrazine） has been synthesized and fully characterized. By self-assembly of the ligand with HgI2, a binuclear complex Hg2I4L（C） was obtained. The structures of L and C were analyzed through single-crystal X-ray diffraction. L crystallizes in monoclinic, space group P21/n with a=11.286（5）, b=3.981（5）, c=23.865（5） , β=100.043（5）°, V=1056（1） 3, Z=4, Dc=1.323 g/m3, F（000）=440, Μr=210.24, μ=0.084 mm（-1）, the final R=0.0928 and w R=0.2867 for 6955 observed reflections with I ＆gt; 2（I）. The complex is of monoclinic system, space group P21/n with a=8.706（5）, b=17.468（5）, c=14.675（5） , β=93.922（5）°, V=2227（2） 3, Z=4, Dc=3.338 g/m3, F（000）=1928, Μr=1119.02, μ=19.321 mm（-1）, the final R=0.0366 and w R=0.1276 for 3920 observed reflections with I ＆gt; 2（I）. The structural analysis revealed that the molecule of L possesses a well planar structure. However, in the complex, the coordinated ligand distorts greatly. The absorption spectra of L and the complex in ethanol were experimentally and theoretically studied. The result indicates that the complex exhibits different absorption spectrum compared with the free ligand.

Metal-induced Coordination Networks Using a C2v-based Hexacarboxylate Ligand:Syntheses, Structures and Properties

Metal-organic frameworks(MOFs), consisting of metal, anion and organic ligands, have attracted much attention. The structure of MOFs is affected by various factors. To explore the effects of metal ions, we synthesized six complexes, namely {[Me2NH2][Zn4(H2L)(L)]·2 H2O·2 DMF}n(1), {[Me2NH2]2[Cd2(L)]·2H2O}n(2), {[Me2NH2]2[Ca3(L)(μ-OH)2(DMF)2]·2H2O}n(3) and {[Me2NH2]2[M2(L)(μ-OH)]· H2O·2DMF}n(M = Co, 4;Ni, 5;Mn, 6), from a C2v-based hexacarboxylate ligand([1,1’;4’,1’’]terphenyl-3,5,2’,5’,3’’,5’’-hexacarboxylic acid(H6L)) using metal-induced strategy. These MOFs were thoroughly characterized by single-crystal and X-ray diffraction, elemental analysis, Fourier-transform infrared spectra(FTIR) and photoluminescence.

Mannich Base Derivatives of 1,2-Benzisothiazolin-3-one: Syntheses, Crystal Structures and Bioactivities

Twelve Mannich base derivatives of 1,2-benzisothiazolin-3-one were synthesized by the reaction of 1,2-benzisothiazol-3（2H）-one （BIT） with different amines and formaldehyde. All the compounds were characterized by elemental analysis, IR spectroscopy, MS and 1H NMR. The crystal structure for 2,2＇-methylenebis（benzo[d]isothiazol-3（2H）-one） （3） has been determined by X-ray single-crystal structure analysis. Compound 3 （C15HIoN202S2） crystallizes in the monoclinic system, space group C2/c with a = 25.052（8）, b = 4.510（1）, c = 11.948（4） A, β = 100.992（4）°, V= 1325.2（7） A3, Mr = 314.37, Dc = 1.576 Mg.m-3, p = 0.25 mm-1, F（000） = 648, Z = 4, R = 0.034 and wR = 0.087. The preliminary biological test indicated that the compounds （2b, 2c） showed growth inhibitory activity against the gram-positive and gram-negative bacteria.

Syntheses, Crystal Structures and Characterization of Two New Cadmium(II) Arsonates

Two cadmium arsonate coordination polymers, Cd（HL1）2 （1, H2L1 = 4-aminophenylarsonatic acid） and Cd（H2L2）2·2H2O （2, H3L2 = 2-（4-arsonphenylamino）acetic acid）, have been synthesized and characterized by IR and single-crystal X-ray diffraction. Crystal data for 1： triclinic, space group P1 with a = 5.7559（12）, b = 7.0903（14）, c = 8.9925（18）, α = 89.04（3）, β = 80.79（3）, γ = 85.09（3）o, Dc = 2.496 g·cm-3, μ = 6.095 mm-1, F（000） = 260, Z = 1, the final R = 0.0574 and wR = 0.1376 for 1489 observed reflections with I 〉 2σ（I）. And those for 2： monoclinic, space group P21/c with a = 4.7595（10）, b = 9.925（2）, c = 22.609（5）, β = 91.81（3）°, Dc = 2.167 g·cm-3, μ = 4.168 mm-1, F（000） = 684, Z = 2, the final R = 0.0335 and wR = 0.0815 for 2340 observed reflections with I 〉 2σ（I）. The structure of 1 shows a two-dimensional layer consisting of inorganic chains of {CdN2（AsO3）2} along the a axis linking with the phenyl groups. These layers are further linked through strong interlayer hydrogen bonding interaction to form a three-dimensional hydrogen bond supramolecular architecture. Compound 2 has inorganic chains of {CdO2（AsO3）2} similar to 1, which connect with four adjacent inorganic chains forming a three-dimensional framework.

Three Nickel/maleonitriledithiolate Complexes Accompanied by Different Organic Molecules: Syntheses, Crystal Structures and Properties

Three complexes [AMP][Ni（mnt）2]·CH3CN （1, AMP = 1-（9-anthrylmethyl）pyri- dinium）, [DPI]2[Ni（nmt）2]I （2, DPI = diphenyliodonium） and [DD][Ni（mnt）2]2·2H2O （3, DD = dimethylenediamine） have been prepared and characterized by elemental analyses and IR spectroscopy. X-ray diffraction studies show that three complexes crystallize in the same triclinic space group Pi, and anionic accumulations are formed in a column shape. The results show that different counter-cations could induce versatile anionic stacks. The structures of three complexes exhibit rich hydrogen bonding interactions. In addition, UV-VIS properties of them are also investigated.

STUDIES ON THE SYNTHESES AND BACTERICIDAL ACTIVITIES OF ACYLAMINOETHYL GLYCINES AND OF THEIR CYCLO-CONDENSATION PRODUCTS

Two series of new compounds:the aliphatic acylaminoethyl glycines (Ⅰ) and their cyclo-condensation products-allphatic acylaminoethyl plperazlnones (Ⅱ) were synthesized.The results of bactericidal and bacteriostatic tests show that the two series of compounds are good bactericldal agents.

SYNTHESES AND SPECTROSCOPIC PROPERTIES OF PORPHYRIN-PHTHALOCYANINE MITH FLEXIBLE POLYATONIC CHAINS

The syntheses of porphyrin-phthalocyanine heterodimers with flexible polyatomic chains especially designed for the studies of intramolecular photoinduced processes are presented along with the effect of mutual orientation of the chromophore subunits on intramolecular energy transfer efficiency.

SYNTHESES OF Ph AND TEMPERATURE－SENSITIVE HYDROGELS AND THEIR APPLICATIONS IN CONTROLLED RELEASE OF BIOMACROMOLECULES

A series of pH- and temperature-sensitive hydrogels were prepared These gels do not swell at 37℃ and pH 1.4 but swell at 37℃ and pH 7 4.When papain was loaded in these gels. it can be released at 37℃ and pH 7 4in a high percentage without any loss of activity.

Syntheses of novel series benzo [1,5] oxazepin-4-one-based compounds from 1,5-difluoro-2,4-dinitrobenzene

A novel benzo [ 1,5] oxazepin-4-one skeleton compound and its four derivatives were synthesized effectively from 1,5-difluoro- 2,4-dinitrobenzene （DFDNB） under mild conditions. In the process, four intermediates were synthesized by substitutions of the two fluorine atoms and reductions of the meta-dinitro groups in DFDNB respectively. The results showed that the key for synthesizing the intermediates was the substitution of one of the two fluorine atoms in DFDNB by 3-hydroxy butyric acid ethyl ester first, then the other fluorine atom by morpholine, and then the reduction of the meta-dinitro groups in the substitute by HCOONH4 with Pd/C. The products were purified with silica gel column chromatography, and confirmed by HPLC, LC-MS and 1H NMR. They should contribute to construct the molecular libraries for therapeutic applications.

Syntheses of (3-Benzyl-4-Aroyl-1,2,4-Triazole-5-yl)[5-(3,4,5-Trimethoxylphenyl)-1,3,4-Oxadizole-2-yl] Sulfides

Twelve new (3-benzyl-4-aroyl-1,2,4-triazole-5-yl)[5-(3,4,5-trimethoxyphenyl)-1,3,4- oxadiazole-2-yl]sulfides(2) have been synthesized from the nucleophilic displacements of 3-benzyl-4- trimethoxyphenyl)-1,3,4-oxadiazole(1). Compounds(2) were screened for their antibacterial activity against E.Coli at 0.01%. The results show that some compounds(2) have strong inhibiting effects

The Syntheses,Characterization and Crystal Structure of Extraction Complexes of Rare Earths

The syntheses,characterization and crystal structure of rare earth coordination compounds of five typical extraction systems commonly used in the separation technology were reported.They are:(1)carboxylic acid system,(2)organophosphorous acid system,(3)quarternary ammonium salt system,(4)neutral organophosphonate system and(5)synergistic system.

SYNTHESES OF TETRAHEDRAL METAL CLUSTER COMPOUNDS

The carbyne compound [Br(CO)_2(Py)_2Mo(≡CC_6H_5)] (Py=pyridine) (1a) reacts with Co_2 (CO)_8, Fe_2(CO)_9 and Mn_2 (CO)_(10) to give tetrahedral tri-metal cluster compounds Co_2Mo(μ_3-CC_6H_5)Br(CO)_8(Py)_2 (2), Fe_2Mo(μ_3-CC_6H_5) Br(CO)_9(Py)_2 (3) and Mn_2Mo(μ_3-CC_6H_5)Br(CO)_(10) (Py)_2 (4) respectively. Tri-metal cluster compound Co_2Mo(μ_3-CC_6H_5)Br(CO)_8-(bipy) (bipy=α,α'dipyridyl) (5) is prepared in a similar reaction sequence from [Br(CO)_2(bipy)Mo(≡CC_6H_5)] (1b) and Co_2(CO)_8. IR, ~1H and ^(13)C NMR spectral data of these compounds are reported and discussed. The crystal structure of compound (5) has been determined by X-ray diffraction.

Syntheses of Ferrocenyl Schiff Bases Using Molecular Sieves and AlCl_3 as Catalysts

In order to study the donor ability of ferrocenylimines as directing ortho metalation group（DMG） to lithium alkylide to prepare planar chiral ferrocene, a series of ferrocenyl schiff bases were synthesized by new methods using molecular sieves（0.4nm） and AlCl3 as catalysts. The reaction periods were reduced using these two catalysts in contrast with Al2O3, which was a traditional method used in the literature. In addition, as an important feature of these schiff bases, we found that they were unstable as oils in air or when filtrated through silica gel, but were stable as solids. The structures of the new compounds were confirmed by IR, ^1H NMR and HRMS.

SYNTHESES AND SPECTRA OF HETEROPOLY BLUES OF DOUBLE 2:17 MOLYBDOPHOSPHATES LANTHANIDE COMPLEXES

The present paper reports eight heteropoty blues of double 2:17 motybdophosphates tanthanide comptexes with tacunary Dawson structure, i.e., K_(17)H_2[Ln(P_2Mo_2~ⅤMo_(15)~ⅥO_(16))_2], nH_2O and K_(17)H_4 [Ln(P_2Mo~Ⅴ_4Mo_(13)~ⅥO_(61))_2], nH_2O(Ln=La, Pr, Sm, Yb). They were characterized by etementat anatyses, potentiometric titration, IR, UV, potarography, cyclic vottammetry, X-ray photoelectron spectra, X-ray powder diffraction, thermat analyses and ESR. The results show that the properties of these heteropoty btues are different from those of heteropoty blues with saturated Dawson structure and other tacunary series. They are more stabte than their parent heteropoty acids in aqueous sotution and have the abitity of anti-base decomposition.

Syntheses, Crystallographic and Magnetic Properties of Nd_3Fe_(29-x)Cr_x and Other Associated Compounds

A systematic study of syntheses and magnetic properties of the Nd_3Fe_(29-x)Cr_x (x=4.5, 4.7, 5.0, and 5.5) compounds has been performed. The single-phase compounds of Nd_3Fe_(29-x)Cr_x can be formed in the range 4.5≤ x ≤ 5.5. The Curie temperature T_C, the saturation magnetization M_s at 4.2 K, the anisotropy field H_A at 4.2 K and room temperature. and the intra-sublattice exchange coupling parameter j_(FeFe) at 4.2 K for the Nd_3Fe_(29-x)Cr_x compounds decrease with increasing Cr composition from x=4.5 to 5.5, respectively. Nitrogenation and carbonation, unlike hydrogenation. result mainly in improvements of the Curie temperature, the saturation magnetization and the anisotropy field at 4.2 K and room temperature for the Nd_3Fe_(29-x)Cr_x compounds compared with their parent compounds.

SYNTHESES AND SPECTROSCOPIC PROPERTIES OF LANTHANIDE COMPLEXES, Ln(acac)_3(Ph_3PO)_3

A series of new complexes of formula Ln(acac)_s(Ph_3PO)_3 (where Ln^(3+)=Nd^(3+), Sm^(3+), Eu^(3+), Tb^(3+), Ho^(3+)) have been prepared and characterized. The coordination of two ligands with lanthanide ions are studied by IR spectra, ~1H, ^(13)C, ^(31)P-NMR and metal-ligand charge tranafer tranaition is also discussed via electronic adaorption and luminescence spectroscopy.