A Three-dimensional Zinc 1,3,5-Benzene-tricarboxylate with Rutile Topology Isolated in DMSO Solvothermal Reaction

A new zinc 1,3,5-benzenetricarboxylate Zn3（BTC）2（DMSO）4（BTC=1,3,5-benzenetricarboxylate） has been solvothermally synthesized in DMSO and structurally determined by X-ray single-crystal diffraction.It crystallizes in the monoclinic system,space group P21/c with a=10.0861（11）,b=10.2527（11）,c=16.4013（18）,β=95.478（2）°,V=1688.3（3）3,Z=2,Zn3S4C26H30O16,Mr=922.85,Dc=1.815 g/cm3,F（000）=936,μ=2.434 mm-1,R=0.0319 and wR=0.0755.This compound consists of trimeric zinc clusters and BTC linkers.Alternate connection of these trimeric zinc clusters and BTC linkers results in a three-dimensional（3,6）-connected frame-work with rutile topology.

Structural Diversity and Photoluminescent Properties of Two Mn(Ⅱ) Sulfoterephthalate Complexes from Multi-pyridine N-containing Ligands

Solvothermal reaction of manganese（II） salt with monosodium 2-sulfoterephthalate（2-NaH2stp） and two multi-pyridine N-containing auxiliary ligands results in the formation of two new complexes formulated with [Mn2（Hstp）2（bpp）2（H2O）4]（1） and [Mn3（stp）2（tpy）3（H2O）]（H2O）5（2）（bpp = benz-2,3-pyrimidine-[2,3-f]-1,10-phenanthroline, tpy = 2,2＇：6＇,2＇＇-terpyridine）. X-ray diffraction structural analyses of two complexes reveal their structural diversity（0D and 1D） due to the difference of auxiliary ligands. 1 is a discrete structure, in which the Mn（Ⅱ） ion is hexa-coordinated with one stp, one bpp ligand and two water molecules. Complex 2 is a one-dimensional（1D） chain-like structure with three crystallographically independent Mn（Ⅱ） ions. The photoluminescent properties could be assigned to the π-π＊ transition of 2-sulfoterephthalate ligands.

Syntheses,Structures and Photoluminescent Properties of Cd(Ⅱ)Polymeric Complexes Based on 5-Aminoisophthalic Acid and Bipyridine Co-ligands

Two novel complexes, namely {[Cd（AIP）（4,4＇-bpy）]·1.3DMF}n（1） and [Cd（AIP）（2,2＇- bpy）]n（2）, have been synthesized through solvothermal reaction（H2AIP = 5-aminoisophthalic acid, 2,2＇-bpy = 2,2＇-bipyridine, 4,4＇-bpy = 4,4＇-bipyridine, and DMF = N,N＇-dimethylformamide） and structurally determined by single-crystal X-ray diffraction. Complex 1 shows a three-dimensional（3D） layer-pillar framework with rectangular channels, while complex 2 displays a two-dimensional（2D） wave net architecture. Furthermore, 1 and 2 were characterized by elemental analysis, infrared spectra（IR）, thermal gravimetric analyses（TGA） and fluorescence measurements. The luminescent properties of 1 dispersed in various organic solvents have been investigated systematically, demonstrating high selectivity for acetone via the fluorescence quenching effect.

3D Supramolecular Network Based on Hydrogen Bonds Between 1D [Ni(μ_2-C_2O_4)(Him)_2] Zigzag Chains

In recent years, considerable attention has been paid to supramolecular networks based on metal organic building blocks because of their potential applications in diverse fields, such as, catalysis, optics, sensors, magnetism, and molecular recognition^[1-3]. On the ba- sis of the principles of crystal engineering and special synthesis strategies, several novel supramolecular frameworks have been assembled from various organic, inorganic and metal-organic moieties, which largely en- riches the structure chemistry of solid state materi-als^[4-9].

Synthesis and Structure of a 3D Manganese Coordination Polymer with 1,3-Bis(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene and 1,5-Naphthalenedisulfonate

The organic-inorganic hybrid polymer [Mn（mbbimb）2（1,5-nds）]n 1 has been synthesized using 1,5-naphthalenedisulfonate （1,5-nds） and 1,3-bis（benzimidazol-1-ylmethyl）- 2,4,structure analysis indicates that 1 crystallizes in monoclinic, space group C2/c with a=21.3546（17）, b=11.8841（7）, c=22.1588（16）A, β=108.058（3）°, C60H54MnN8O6S2, Mr=1102.17, Z=4, V=5346.5（7）A^3, Dc=1.369 g/cm^3, μ=0.386 mm^-1, F（000）=2300, S=1.091, R=0.0634 and wR=0.1559 for 4641 observed reflections （I 〉 2σ（I））. The Mn center is six-coordinated to furnish a distorted octahedral geometry, and the overall framework is a 6-connected 3D net.

Two New Coordination Complexes Based on Eosin Y Dye Ligand：Syntheses,Crystal Structures and Magnetic Properties

Two novel coordination compounds formulated as [Co2（EY）2（L1）]·2C2H5OH（1） and [Mn2（EY）2（L1）]·2C2H5OH（2）（EY = Eosin Y dianion, L1 = 4,4＇-bipyridine） based on Eosin Y dye ligand have been prepared by solvothermal reactions and structurally characterized. Single-crystal X-ray diffraction studies reveal that compounds 1 and 2 are isostructural. They show weak antiferromagnetic coupling between the adjacent Co^Ⅱ and Mn^Ⅱ ions, respectively.

Cadmium(Ⅱ) Nitrite Complex Based on the Bis(2-benzimidazole) and Aromatic Carboxylate Ligands

A new cadmium（Ⅱ） nitrite complex Cd2（H2C3PIm）2（BDC）（NO2）2（1,H2C3PIm = 2,2＇-（1,3-propanediyl）bis（1H-benzimidazole）,H2BDC = 1,4-benzenedicarboxylic acid） has been synthesized by solvothermal reaction in formamide,and its structure（C42H36Cd2N10O8,Mr = 1033.61） was determined by single-crystal X-ray diffraction analysis.The crystal belongs to the monoclinic system,space group P21/n with a = 0.9859（5）,b = 0.8936（5）,c = 2.3188（5） nm,β = 97.576（5）°,V = 2.025（16） nm3,Z = 2,Dc = 1.695 g/cm3,μ（MoKα） = 1.118 mm-1,F（000） = 1036,S = 1.017,the final R = 0.0304 and wR = 0.0752 for 3761 reflections with I 〉 2σ（I）.The centrosymmetric complex 1 contains a dimer in which two distorted octahedral Cd（II） centers are bridged by BDC ligand and chelated by H2C3PIm.The units of the complex are linked via weak N-H···O hydrogen bonds between the nitrito and the BDC ligands,leading to the formation of a 1D zigzag chain along the b axis.The π-π packing interactions contribute to the formation of a three-dimensional supramolecular architecture.The complex exhibits strong photoluminescence at room temperature.

Synthesis,Crystal Structure and Photoluminescence of a One-dimensional Zinc(Ⅱ)Coordination Polymer with Substituted Terpyridine

The title compound, [Zn（4-pytpy）（NO3）2] （4-pytpy = 4′-（4-pyridyl）-2,2′：6′,2＂- terpyridine） 1, has been synthesized by the solvothermal reaction of Zn（NO3）2·6H2O with 4-pytpy in CH3OH solution. It crystallizes in the triclinic system, space group P1 with a = 8.358（6）, b = 11.121（8）, c = 11.374（8）A, α = 74.226（11）, β = 74.532（11）, γ = 83.085（12）°, Mr= 499.74, V= 979.3（12） A3, Z = 2, Dc = 1.695 g/cm3, F（000） = 508,μ = 1.309 mm^-1, the final R = 0.0547 and wR = 0.1588. X-ray crystal structure analysis revealed that the Znn is hexa-eoordinated by two oxygen atoms from two nitrate groups and four nitrogen atoms, three of which are from the tridentate domain of one 4-pytpy and the other from the monodentate domain of another 4-pytpy. 4-pytpy as a bridging ligand connects ZnⅡ into a one-dimensional coordination polymer.

Solvothermal-induced construction of ultra-tiny Fe_(2)O_(3) nanoparticles/graphene hydrogels as binder-free high-capacitance anode for supercapacitors

Three-dimensional(3D) ultra-tiny Fe_(2)O_(3) nanoparticles/graphene hydrogels were prepared using a facile and efficient solvothermal reaction, by which the phase of iron oxide, particle size and the morphology of hydrogels can be precisely controlled by simply adjusting the solvothermal reaction time. Accordingly, the effect of the microstructures of hydrogels on electrochemical performance was systematically studied. It was found that Fe_(2)O_(3)/r GO-50 hydrogels(with a solvothermal reaction time of 50 min) possessed a desirable crystallinity, suitable particle size, decent porous structure, large specific surface area and high electrical conductivity, thus exhibiting a superior electrochemical performance as binder-free anode of supercapacitors: a large potential range of 1.15 V, an ultrahigh specific capacitance of 1090 F·g^(-1) at a current density of 2A·g^(-1) and excellent rate capability (531 F·g^(-1) at 10 A·g^(-1)). The rational design and systematic research of electrode materials will provide new lights for the preparation of advanced electrochemical energy storage devices.

Solvothermal-assisted morphology evolution of nanostructured LiMnPO_4 as high-performance lithium-ion batteries cathode

As a potential substitute for LiFePO4, LiMnPO4 has attracted more and more attention due to its higher energy, showing potential application in electric vehicle（EV） or hybrid electric vehicle（HEV）. In this work,solvothermal method was used to prepare nano-sized LiMnPO4, where ethylene glycol was used as solvent, and lithium acetate（LiAc）, phosphoric acid（H3 PO4） and manganese chloride（MnCl2） were used as precursors. The crystal structure and morphology of the obtained products were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The electrochemical performance was evaluated by charge-discharge cycling, cyclic voltammetry and electrochemical impedance spectroscopy. The results show that the molar ratio of LiAc：H3 PO4：MnCl2 plays a critical role in directing the morphology of LiMnPO4. Large plates transform into irregular nanoparticles when the molar ratio changes from 2：1：1 to 6：1：1. After carbon coating, the product prepared from the 6：1：1 precursor could deliver discharge capacities of 156.9,122.8, and 89.7 mAhg-1 at 0.05 C, 1 C and 10 C, respectively.The capacity retention can be maintained at 85.1% after 200 cycles at 1 C rate for this product.

Direct synthesis of hollow polyhedral ceria nano powders via a template-free mixed solvothermal route

Novel mono-dispersed hollow polyhedral ceria nano powders with the average particle size of 250 nm were directly synthesized via a simple template-free mixed solvothermal method by using water-ethanol as the solvent. The formation of such hollow structure with the regular polyhedral particle shape was based on a solvent-controlled Ostwald ripening coupled self-templating process. The mixed solvent promoted the formation of the regular solid particles at the beginning of solvothermal reaction and drove the Ostwald ripening as the reaction went on. Owing to the Ostwald ripening and self-assembly of nano crystallites, ceria nano particles converted into the hollow structures with regular polyhedral shape during the solvothermal process just by increasing solvothermal reaction time. The as-synthesized hollow ceria nano powders exhibited strong absorptions in the UV-vis spectrum and the evaluated energy band gaps increased according to the shape evolution and size decrease of the nano particles, which demonstrated obvious blue shift effects.

Influence of the Metal Ions on the Allylic Rearrangement Reac- tion of 3,4,5,6-Tetrahydrophthalic Anhydride

To further investigate the influence of metal ions on the allylic rearrangement of 3,4,5,6-tetrahydrophthalic an- hydride during the hydrothermal reaction, metal ions such as manganese（Ⅱ）, zinc（Ⅱ） and cadmium（Ⅱ） have been employed in the synthesis, which leads to the formation of three new lamellar coordination polymers, [MnⅡs（μ3-OH）3（1-chec）（1,2-chedc）（2,3-chedc）2（H20）] （3Mn）, [ZnⅡs（μ3-OH）3（1-chec）（1,2-chedc）（2,3-chedc）2（H20）] （4Zn）, and [CdⅡ3（μ3-OH）2（1,2-chedc）2] （5Cd） （1-chec=cyclohexene-l-carboxylate, 1,2-chedc=cyclohexene-1,2- dicarboxylate, 2,3-chedc=cyclohexene-1,2-dicarboxylate）. Interestingly, the allylic rearrangement reaction is metal-dependent, which occurs only in 3Mn and 4Zn, resulting in the formation of one chiral carbon atom of the corresponding dicarboxylate ligands in both compounds. In addition, the magnetic property of compound 3Mn was studied, which revealed strong antiferromagnetic interactions between the metal centers.

Adsorption and Visible Light Photocatalytic Degradation of Electrospun PAN@W_(18)O_(49) Nanofibers

Low density and high porosity polyacrylonitrile(PAN)nanofibers prepared by electrospinning were used as brackets for photocatalyst W_(18)O_(49) to prepare a kind of light weight and easy recycling water purification material for the first time.The influence of tungsten source concentration on the formation of W_(18)O_(49) during a solvothermal process was systematically investigated.The prepared PAN@W_(18)O_(49) nanofibers(NFs)utilize the outstanding visible light photocatalytic performance and the adsorption performance of W_(18)O_(49),and at the same time give the advantages of low density and easy recyclability.The pollutant removal performance of the composite nanofibers was investigated by using five contaminants including rhodamine B(RhB),methylene blue(MB),malachite green(MG),methyl orange(MO)and chlortetracycline(CTC)as substrates.Among them,the degradation process of rhodamine B has been studied in detail.After five cycles,the degradation efficiency did not decrease significantly,showing excellent reusability of PAN@W_(18)O_(49) NFs.Besides,the adsorption performance of PAN@W_(18)O_(49) NFs during the photocatalytic process was also studied in detail.Compared with recently reported literature,the degradation efficiency of organic pollutants by PAN@W_(18)O_(49) NFs showed better performance,and PAN@W_(18)O_(49) NFs felt had a promising prospect in the field of degradation of contaminants.

Synthesis of CdS Nanowires on Cd Foil and Their Photoluminescence Properties

Cadmium sulfide （CdS） nanowires were synthesized on Cd foil via a simple solvothermal reaction at 180℃ using thiosemicarbazide as the sulfide source and ethylenediamine as the solvent. The CdS nanowires are hexagonal-phase single crystals with an average diameter of 50 nm and length of several microns. The as-prepared CdS nanowires show an absorption peak of around 483 nm in the absorption spectrum. The CdS nanowires exhibit bright photoluminescence （PL） with two distinct emission bands at 503 nm and 697 nm, which shows that the as-prepared CdS nanowires are high-quality nanocrystals.