Complex coordinated functional groups[MA_(x)B_(y)](M=Central coordination element;A,B=P,O,S,Se,F,Cl,Br or I)are composed of different types of anions A,B jointly linked to the same central cation M,which are in high p...Complex coordinated functional groups[MA_(x)B_(y)](M=Central coordination element;A,B=P,O,S,Se,F,Cl,Br or I)are composed of different types of anions A,B jointly linked to the same central cation M,which are in high potential to tune the physical properties of materials,e.g.,second-order susceptibility,energy gaps and birefringence.Recently,Compound containing complex coordinated functional groups have attracted great attention in the nonlinear optical(NLO)field and a large number of this type crystals exhibit promising NLO performance.However,the inherent relationship between ionic group structure and optical properties of complex coordinated NLO materials have not been systematically studied.This article systematically summarizes complex coordinated NLO materials in recent five years from the perspective of the internal relationship between crystal structure and optical properties.In addition,we propose the ideal combination and arrangement modes for structural building units,and also reveal the influence of complex coordinated functional groups[MA_(x)B_(y)]toward the NLO response,optical band gap and phase matching ability of complex coordinated NLO materials.展开更多
With the increase of people’s demand,it is extremely desired for developing high-safety,widetemperature-range and high-energy-density lithium batteries,but huge challenges are remained due to shrinkage and combustion...With the increase of people’s demand,it is extremely desired for developing high-safety,widetemperature-range and high-energy-density lithium batteries,but huge challenges are remained due to shrinkage and combustion of commonly used polyolefin separators at high temperatures,as well as narrow usable temperature range and high flammability of conventionally commercialized liquid electrolytes.In this work,we report a multifunctional separator mainly consisting of Zn^(2+)-phytate coordination complex nanoparticles and bacterial cellulose nanofibers,named the BZP separator,which possesses high porosity,excellent thermotolerance,good flame retardancy,abilities of anion binding and Ni^(2+)capturing.Through cooperating with the fluoride-free wide-temperature-range electrolyte,Li//LiFePO_(4) cells not only deliver discharge capacities of 110.39 mA h g^(-1)and 113.25 mA h g^(-1)after 2200 cycles (2 C) and1600 cycles (5 C) at 25℃,with capacity retentions of 76.59%and 86.09%,respectively,but also exhibit excellent cycling performance at 80℃ and-40℃.Significantly,the Li//NCM811 cell with a loading of7.8 mg cm^(-2)delivers a discharge capacity of 146.64 mA h g^(-1)after 200 cycles at 0.5 C,with a capacity retention of 89.03%.In addition,pouch cells can work at 120℃ and have low flammability.展开更多
Narrow solar-light response range and rapid charges recombination are the main technical barriers in TiO_(2) photocatalysis technology.To overcome these restrictions,in this work we synthesized a novel binuclear gadol...Narrow solar-light response range and rapid charges recombination are the main technical barriers in TiO_(2) photocatalysis technology.To overcome these restrictions,in this work we synthesized a novel binuclear gadolinium(Ⅲ) coordination complex,[Gd_(2)(DPDB)_6(DMF)_6(H_(2)O_()2)](DPDB=[(4-dimethylamino)phenyldiazenyl] benzenesulfonate),which was used as an inorganic sensitizer for boosting the visible light-harvesting and quantum efficiency of TiO_(2) supported-reduced graphene oxide(rGO) nanocomposite.Crystal structure of [Gd_(2)(DPDB)_6(DMF)_6(H_(2)O)_(2)](Gd-CMP) was determined from single-crystal X-ray diffraction data,which indicates three-dimensional(3D) supramolecular architecture through hydrogen bonding and CH…π_(ph) interactions.The prepared nanohybrid(Gd-CMP/TG) reveals significantly enhanced visible-light-induced photocatalytic activity for degradation of acetaminophen(ACT).The complete removal of 10 mg/L ACT is achieved over Gd-CMP/TG,and the corresponding rate constant of ACT degradation of nanohybrid is 40-fold higher than that of bare TiO_(2).In prepared ternary nanohybrid,metal-coordination sensitizer(Gd-CMP) acts as an electron donor,and at the same time,rGO serves as an electron acceptor,and the synergistic effect between them efficiently enhances charges separation and inhibits e/h pair recombination in the hybridized species.The radical scavenger tests indicate that the photo-induced O_(2)^(-·) radicals dominate ACT degradation.On the basis of the experimental results and calculated energy of electronic levels,a possible mechanism for the improved photocatalytic activity is discussed.展开更多
With the development of coal chemical industry,large amounts of naphthalene and n-butene are produced,and converting them into high value-added products through alkylation has gained particular importance and interest...With the development of coal chemical industry,large amounts of naphthalene and n-butene are produced,and converting them into high value-added products through alkylation has gained particular importance and interest.In this work,liquid coordination complexes(LCCs)were used as acid catalysts for the first time in the naphthalene alkylation reaction under mild conditions to obtain multibutylnaphthalenes with high yield.Various reaction conditions were thoroughly investigated.The LCC consisting of urea and AlCl_(3) showed excellent catalytic performance under optimal reaction conditions,giving 100%conversion of naphthalene and 99.66%selectivity towards multi-butylnaphthalenes.Combining the catalyst properties and catalytic results,a plausible reaction mechanism was proposed.The lubricating properties of the synthesized products were investigated for their potential application as lubricating base oils.The synthesized multi-butylnaphthalenes showed comparable physicochemical properties and tribological performances as the commercial cycloalkyl base oil.展开更多
Two 1D coordination polymers [Ln2（dpdc）3（tpy）2·H2O]n [Ln=Nd 1, Yb 2, H2dpdc=2,2＇-biphenyldicarboxylic acid and tpy= 2,2＇：6＇,2＇＇-terpyridine] and one dinuclear complex Er2（dpdc）2（Hdpdc）2（tpy）2 3 we...Two 1D coordination polymers [Ln2（dpdc）3（tpy）2·H2O]n [Ln=Nd 1, Yb 2, H2dpdc=2,2＇-biphenyldicarboxylic acid and tpy= 2,2＇：6＇,2＇＇-terpyridine] and one dinuclear complex Er2（dpdc）2（Hdpdc）2（tpy）2 3 were obtained via hydrothermal reactions and determined by X-ray diffraction analysis. The crystal structure data of 1 and 2 revealed that two coordination polymers were isostructural and possessed a 1D chain framework consisting of eight-coordinated Ln（III） centers. In the asymmetric unit, the two Er（III） ions in 3 were both nine-coordinated and had similar coordination environments. The Er（III） ions were bridged by dpdc2-ligands into dinuclear structures. The complexes were also characterized by IR spectra and thermogravimetric analysis. The solid fluorescence of 1 and 3 was also investigated at room temperature.展开更多
Two coordinate reactions,NdCl 3·6H 2O(s)+3CCl 3COOH(s)(or TCA)=Nd(TCA)3·3H 2O(s)+3HCl(g)+3H 2O(l)and Nd(TCA)3·3H 2O(s)+2C 9H 7NO(s)=Nd(TCA)(C 9H 6NO)2(s)+2CCl 3COOH(s)+3H 2O(l),were studied by the class...Two coordinate reactions,NdCl 3·6H 2O(s)+3CCl 3COOH(s)(or TCA)=Nd(TCA)3·3H 2O(s)+3HCl(g)+3H 2O(l)and Nd(TCA)3·3H 2O(s)+2C 9H 7NO(s)=Nd(TCA)(C 9H 6NO)2(s)+2CCl 3COOH(s)+3H 2O(l),were studied by the classical solution calorimetry at 298.15K.The molar dissolution enthalpies of the reactants and the products in certain solvent(the first reaction in 1 mol·L-1 HCl,the second in a mixed solution consisting of absolute ethyl alcohol,dimethyl sulfoxide and 4 mol·L-1 HCl)were measured by using an isoperibol calorimeter at 298.15K.From the results and other auxiliary quantities,the standard molar formation enthalpies of[Nd(TCA)3·3H 2O,s,298.15K]and[Nd(TCA)(C 9H 6NO)2,s,298.15K]are determined asΔfH m°[Nd(TCA)3·3H 2O,s,298.15K]=-3053.3 kJ·mol-1 andΔfH m°[Nd(TCA)(C 9H 6NO)2,s,298.15K]=-1355.6 kJ·mol-1.展开更多
A new coordination complex [Cd(pda)(pyz)(H2O)2]n(1, H2 pda = 1,4-phenylenediacetic acid, pyz = pyrazine) have been synthesized and structurally characterized. Crystal data for the title complex are as follows: orthorh...A new coordination complex [Cd(pda)(pyz)(H2O)2]n(1, H2 pda = 1,4-phenylenediacetic acid, pyz = pyrazine) have been synthesized and structurally characterized. Crystal data for the title complex are as follows: orthorhombic system, space group Ccmb with a = 11.5245(3) b = 19.5069(5) c = 11.4231(3) A, V = 2568.00(12) A3, Mr = 188.31, Z = 16, F(000) = 1480, Dc = 1.948 g/cm3, μ(Mo Kα) = 1.725 mm-1, R = 0.0195 and w R = 0.0462 for 1357 observed reflections with I 】 2σ(I). In the title complex, the central Cd(II) ion is located in a distorted octahedral coordination environment. Two Cd(II) ions are bridged by two pda2- ligands and one pyz ligand to form a bi-loop structure. Luminescent property of the complex has also been studied.展开更多
The reactions of Co（C1O4）2·6H2O and Co（NO3）2.6H2O with the di-Schiff base ligand N,N＇-bis-（1-benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine （LA） in ethanol have been investigated. The reactions of LA wi...The reactions of Co（C1O4）2·6H2O and Co（NO3）2.6H2O with the di-Schiff base ligand N,N＇-bis-（1-benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine （LA） in ethanol have been investigated. The reactions of LA with excess amount of cobalt salts yield the six-coordinate complexes [CoL2]（ClO4）E·H2O 1 and [CoL2]（NO3）E·H2O 2 as isolatable products （L= N-（1- benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine）, where L is a tri-dentate mono-Schiff base ligand, resulting from the hydrolysis of the precursor di-Schiff base LA. Both complexes were characterized by X-ray crystallography. Crystal data for complex 1： monoclinic, space group P21/c, a = 11.9214（10）, b = 23.5828（17）, c = 14.0387（12）A, β = 135.219（4）°, C22H30Cl2CoN8O9, Mr = 680.37, V = 2780.1（4） A^3 ,Z = 4, Dc = 1.625 g/cm^3,μ（MoKa） = 0.876 mm^-1, F（000） = 1404, the final R = 0.0725 and wR = 0.1530 for 5726 observed reflections （I 〉 2σ（I））. Crystal data for complex 2： monoclinic, space group P21/c, a = 18.2162（16）, b = 10.0610（6）, c = 18.593（2）A, β = 130.099（3）°, C22H30CoN10O7, Mr = 605.49, V = 2606.5（4） A3 Z = 4, Dc = 1.543 g/cm^3,μ（MoKa） = 0.722 mm^-1, F（000） = 1260, the final R = 0.0619 and wR = 0.1429 for 5194 observed reflections （I 〉 2σ（I））. X-ray diffraction analysis reveals that each cobalt atom in the two complexes is chelated by six nitrogen atoms from two tridentate iigands L, exhibiting a slightly distorted octahedral coordination sphere. In both complexes, the strong hydrogen-bonding interactions between the lattice waters and N-H groups of the ligands result in 1D chains which are further connected by ClO4^- （or NO3^-） groups to form a 3D framework. In complex 2, the strong π-π interactions increase the stability of the structure.展开更多
The formation of coordinated dimeric complexes bridged by axial ligands on surface is observed with the help of a 1,3,5-tris（10-carboxydecyloxy）benzene（TCDB） template through scanning tunneling microscopy（STM）. ...The formation of coordinated dimeric complexes bridged by axial ligands on surface is observed with the help of a 1,3,5-tris（10-carboxydecyloxy）benzene（TCDB） template through scanning tunneling microscopy（STM）. STM images of molecular adlayers of zinc tetraphenylporphyrin（Zn TPP）, zinc phthalocyanine（Zn Pc）, and their mixture are reported. Zn TPP and Zn Pc can spontaneously form highly an ordered structure with a 1：1 molar ratio, which is different from that of individual Zn Pc. The coordinated bimolecular complexes bridged with axial ligands, simply as Zn Pc–DPP–Zn TPP and Zn Pc–DPE–Zn Pc, are presented and the corresponding surface structures are compared. Zn Pc and Zn TPP can be connected by an axial ligand DPP and formed assembled structures out of surface. Two types of arrays with entirely new structure are obtained for the Zn Pc–DPE–Zn Pc complex. These bridged hybrid complexes provide an example of design of self-organized crystals on the basis of coordination through non-covalent interactions.展开更多
Chitosan–metal complexes have been widely studied in wastewater treatment, but there are still various factors in complex preparation which are collectively responsible for improving the adsorption capacity need to b...Chitosan–metal complexes have been widely studied in wastewater treatment, but there are still various factors in complex preparation which are collectively responsible for improving the adsorption capacity need to be further studied. Thus, this study investigates the factors affecting the adsorption ability of chitosan–metal complex adsorbents, including various kinds of metal centers, different metal salts and crosslinking degree. The results show that the chitosan–Fe（ Ⅲ） complex prepared by sulfate salts exhibited the best adsorption efficiency（100%） for various dyes in very short time duration（10 min）, and its maximum adsorption capacity achieved 349.22 mg/g. The anion of the metal salt which was used in preparation played an important role to enhance the adsorption ability of chitosan–metal complex. SO4^（2-） ions not only had the effect of crosslinking through electrostatic interaction with amine group of chitosan polymer, but also could facilitate the chelation of metal ions with chitosan polymer during the synthesis process.Additionally, the p H sensitivity and the sensitivity of ionic environment for chitosan–metal complex were analyzed. We hope that these factors affecting the adsorption of the chitosan–metal complex can help not only in optimizing its use but also in designing new chitosan–metal based complexes.展开更多
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 s...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.展开更多
By simulating the electron paramagnetic resonance （EPR） and optical spectra on the basis of the 120 × 120 complete energy matrix, this paper determines the local lattice structure parameters R1 and R2 for MCl...By simulating the electron paramagnetic resonance （EPR） and optical spectra on the basis of the 120 × 120 complete energy matrix, this paper determines the local lattice structure parameters R1 and R2 for MCl：V2＋ （M=Na, K, Rb） systems at 77K, 195 K and RT （room temperature 295 K or 302 K）, respectively. The theoretical results indicate that there exists a compressed distortion in MCl：V2＋ systems. Meanwhile, it finds that the structure parameters R1, R2 and ｜△R｜（ = R1 - R2） increase with the rising temperature. Subsequently, from the analysis it concludes that the relation of EPR parameter D vs. △R is approximately linear. Finally, the effects of orbital reduction factor k on the g factors for the three systems have been discussed.展开更多
Two new transition metal compounds, [Mn（dpa）2（tmd）2]n （1, H2dpa = 4-hydroxy-phenyl-acetic acid, tmd = 4,4-trimethylenedipyridine） and [Co4（dpa）6（tmd）4（H2O）4]n·nH2O·nCl2 （2）, have been synthesiz...Two new transition metal compounds, [Mn（dpa）2（tmd）2]n （1, H2dpa = 4-hydroxy-phenyl-acetic acid, tmd = 4,4-trimethylenedipyridine） and [Co4（dpa）6（tmd）4（H2O）4]n·nH2O·nCl2 （2）, have been synthesized by hydrothermal synthesis. Compound 1 crystallizes in the monoclinic system, space group P21/n with a = 9.828（3）, b = 17.493（5）, c = 11.616（4）, β = 110.146（6）o, V = 1874.9（10）3, C42H42MnN4O6, Mr = 753.74, Z = 2, Dc = 1.335 g/cm3, μ = 0.406 mm-1, F（000） = 790, the final R = 0.1047 and wR = 0.2021 for 2698 observed reflections （I 〉 2σ（I））. Compound 2 crystallizes in the monoclinic system, space group P21/c with a = 11.7214（13）, b = 17.1582（19）, c = 24.625（3）, β = 103.055（3）o, V = 4824.4（9）3, C100H104Cl2Co4N8O23, Mr = 2094.55, Z = 2, Dc = 1.443 g/cm3, μ = 0.809 mm-1, F（000） = 2180, the final R = 0.0550 and wR = 0.0673 for 4104 observed reflections （I 〉 2σ（I））. These complexes were characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. The structural analyses show that the two compounds are both one-dimensional chain structures. However, compounds 1 and 2 form threedimensional supramolecular structures by hydrogen bonds, respectively.展开更多
Two new cobalt（II） coordination complexes, namely [Co（HL）2（biim）（H2O）2]n·n H2O（1） and [Co（Et L）2（biim）]n·3 n（H2O）·2 n（Et HL）（2）（H2L =（fluorene-9,9-diyl）dipropanoic acid, biim = 1,...Two new cobalt（II） coordination complexes, namely [Co（HL）2（biim）（H2O）2]n·n H2O（1） and [Co（Et L）2（biim）]n·3 n（H2O）·2 n（Et HL）（2）（H2L =（fluorene-9,9-diyl）dipropanoic acid, biim = 1,3-bis（imidazol-1-yl）butane）, have been synthesized using the same starting reactants but different solvent medium. The two complexes exhibit distinctly different structures. Compound 1 exhibits a one-dimensional linear chain structure. However, complex 2 reveals a one-dimensional zigzag chain structure. Thermogravimetric analyses（TGA） and luminescent properties of these two complexes have been discussed.展开更多
The 1-D chain coordination complex of {[Mn2（HCAM）3（H2bipy）]·5H2O}n （H3CAM = 4-hydroxypyridine-2,6-dicarboxylic acid, bipy = 4,4＇-bipyridine） has been synthesized by the reaction of 4-hydroxypyridine-2,6-di...The 1-D chain coordination complex of {[Mn2（HCAM）3（H2bipy）]·5H2O}n （H3CAM = 4-hydroxypyridine-2,6-dicarboxylic acid, bipy = 4,4＇-bipyridine） has been synthesized by the reaction of 4-hydroxypyridine-2,6-dicarboxylic acid, 4,4＇-bipyridine and manganese carbonate under hydrothermal conditions, and its crystal structure was determined by X-ray diffraction method The crystal belongs to the monoclinic system, space group P21/n with a = 10.110（2）, b = 20.159（4）, c = 17.861（4）A,β = 99.67（3）°, V = 3.5884（12） nm3, Mr= 901.47, Z = 4, Dc= 1.669 g.cm^-3, μ= 0.798 mm^-1, F（000） = 1840, the final R = 0.0713 and ωR = 0.1853. The complex forms a 1-D chain bridged by HCAM, protonated 4,4-bipyridines link the 1-D chains to construct 2-D networks via N-H...O hydrogen bonds, and networks are further extended via π-π stacking and hydrogen bonds into 3-D supramolecular framework.展开更多
In atomic,molecular,and nuclear physics,the method of complex coordinate rotation is a widely used theoretical tool for studying resonant states.Here,we propose a novel implementation of this method based on the gradi...In atomic,molecular,and nuclear physics,the method of complex coordinate rotation is a widely used theoretical tool for studying resonant states.Here,we propose a novel implementation of this method based on the gradient optimization(CCR-GO).The main strength of the CCR-GO method is that it does not require manual adjustment of optimization parameters in the wave function;instead,a mathematically well-defined optimization path can be followed.Our method is proven to be very efficient in searching resonant positions and widths over a variety of few-body atomic systems,and can significantly improve the accuracy of the results.As a special case,the CCR-GO method is equally capable of dealing with bound-state problems with high accuracy,which is traditionally achieved through the usual extreme conditions of energy itself.展开更多
The ligand o-phenylenediamine (opda) and its oxidized form, o-benzoquinonediimine (bqdi), act as a fascinating candidate coordinating toward transition metal ions leading to the photochemical hydrogen production in ab...The ligand o-phenylenediamine (opda) and its oxidized form, o-benzoquinonediimine (bqdi), act as a fascinating candidate coordinating toward transition metal ions leading to the photochemical hydrogen production in absence of photosensitizers. Herein, we report the systematic study of the interaction between the oxidized form bqdi ligand, tris-(o-benzoquinonediimine) with divalent first-row transition metal series using DFT calculations. The lowest energy structures, bond length, binding energies, frontier molecular orbital analysis, natural bond orbitals, and global reactivity descriptor were calculated using B3LYP/6-311G(d,P) level of theory. The time dependent-DFT at the CAM-B3LYP/6-311+G(d,p) level of theory was applied to determine the electronic structures and the optical spectra. The theoretical binding trend of the divalent first-row transition metal series is decreasing as follows: Cu >Ti > V > Co > Ni > Fe > Cr > Zn >Mn. Among them, the binding potency of iron (II) by the bqdi ligand was not predominantly sturdy as compared to other first-row divalent transition metal ions. The origin of strong coordination with Fe(II) is attributed to its extra capability to induce covalent coordination of bqdi ligands. The complex exhibited two strong peaks at 370 nm and 452 nm, due to the HOMO-3 to LUMO+1 and HOMO-1 to LUMO transitions, respectively. Natural bond orbital analysis showed that the major interaction happens between the N lone pair electrons of the ligand with an anti-bonding orbital of metal ions, in which Ti showed the highest interaction energy than other metal ions. The present systemic DFT study of bqdi ligands with the first-row transition metals strongly encourages the future establishment of photochemical hydrogen production in absence of photosensitizers.展开更多
A novel coordination complex,{[Cd）2（C（20）H（10）O5）2（H2O）4]·10H2O}n,has been synthesized based on fluorescein（2-（6-hydroxy-3-oxo-3 H-xanthen-9-yl） benzoic acid） and systematically characterized by elem...A novel coordination complex,{[Cd）2（C（20）H（10）O5）2（H2O）4]·10H2O}n,has been synthesized based on fluorescein（2-（6-hydroxy-3-oxo-3 H-xanthen-9-yl） benzoic acid） and systematically characterized by elemental analysis,infrared（IR） spectrum,thermo gravimetric analysis（TGA）,powder X-ray diffraction（PXRD） and single-crystal X-ray diffraction.Compound 1 crystallizes in monoclinic,space group P2/n with a = 20.428（5）,b = 8.084（2）,c = 21.689（5）A,β = 96.360（5）°,Mr = 993.46,V = 3559.7（15）A^3,Z = 4,Dx = 1.845 g/cm^3,μ = 1.276 mm^-1,F（000） = 1974,GOOF = 1.044,λ（Mo Kα） = 0.71073 ？,the final R = 0.0553 and wR = 0.1720 for 7245 observed reflections with I 〉 2σ（I）.展开更多
The reaction of the reduced Schiff base HL（N-（4-hydroxybenzyl）-L-serine） with Zn（CH3COO）2·2H2O in aqueous solution afforded [Zn（L）2]·3H2O（I）. The complex has been characterized by elemental analysi...The reaction of the reduced Schiff base HL（N-（4-hydroxybenzyl）-L-serine） with Zn（CH3COO）2·2H2O in aqueous solution afforded [Zn（L）2]·3H2O（I）. The complex has been characterized by elemental analysis, FT-IR, powder X-ray diffraction, electrospray ionization mass spectrometry and single-crystal X-ray diffraction. Complex I crystallizes in the orthorhombic system, space group P212121, with a=9.197（2）, b=10.445（2）, c=24.149（5） , V=2319.8（8） 3, Z=4, C（20）H（30）N2O11 Zn, Mr=539.83, Dc=1.546 g·cm3, μ=1.122 mm（-1）, F（000）=1128, GOOF=0.971, the final R=0.0206 and w R=0.0506 for 4346 observed reflections（I ＆gt; 2σ（I））. In complex I, each Zn（II） ion coordinates with three carboxyl oxygen atoms and two amine nitrogen atoms from three L-anions, forming a distorted five-coordinated trigonal bipyramidal geometry. Complex I exhibits a 1D wavy chain structure that is extended by hydrogen-bonding interactions to form a supramolecular network. The bioactivity of the complex as a potential PTPs inhibitor in vitro was investigated, displaying potent inhibition against PTP1B（IC（50）, 0.24 μM） and TCPTP（IC（50）, 0.53 μM） with a moderate selectivity.展开更多
Two new hydrostable two-dimensional(2 D)uranyl coordination complexes[(UO_(2))_(5)(μ_(3)-O)_(2)(nbca)_(2)].7 H_(2)O(1)and[(UO_(2))_(3)(nbca)_(2)(H_(2)O)_(3)]·2 H_(2)O(2)(H_(3)nbca=5-nitro-1,2,3-benzenetricarboxy...Two new hydrostable two-dimensional(2 D)uranyl coordination complexes[(UO_(2))_(5)(μ_(3)-O)_(2)(nbca)_(2)].7 H_(2)O(1)and[(UO_(2))_(3)(nbca)_(2)(H_(2)O)_(3)]·2 H_(2)O(2)(H_(3)nbca=5-nitro-1,2,3-benzenetricarboxylic acid)were hydrothermal synthesized.Single-crystal structural refinements reveal that both of the two complexes were formed by the packing of 2D uranyl coordination sheets via the hydrogen bonds.The nbca ligand coordinating to the uranyl polyhedron centers constructed the 2D sheets.There are UO8 hexagonal bipyramids and UO7 pentagonal bipyramids in 1 while only U07 pentagonal bipyramids in 2.Photocatalytic degradation of rhodamine B(RhB)in aqueous solution was studied.Complex 2 possesses better performance than 1 with 96.2%of the RhB was degraded in only 60 min.Mechanism studies reveal that the dissolved oxygens are essential to the RhB degradation.The photocurrent density of 2 is more stable than that of 1,which indicating the stronger ability to separate photoexcited electrons and hole pairs of 2.展开更多
基金supported by National Natural Science Founda-tion of China(No.51972208).
文摘Complex coordinated functional groups[MA_(x)B_(y)](M=Central coordination element;A,B=P,O,S,Se,F,Cl,Br or I)are composed of different types of anions A,B jointly linked to the same central cation M,which are in high potential to tune the physical properties of materials,e.g.,second-order susceptibility,energy gaps and birefringence.Recently,Compound containing complex coordinated functional groups have attracted great attention in the nonlinear optical(NLO)field and a large number of this type crystals exhibit promising NLO performance.However,the inherent relationship between ionic group structure and optical properties of complex coordinated NLO materials have not been systematically studied.This article systematically summarizes complex coordinated NLO materials in recent five years from the perspective of the internal relationship between crystal structure and optical properties.In addition,we propose the ideal combination and arrangement modes for structural building units,and also reveal the influence of complex coordinated functional groups[MA_(x)B_(y)]toward the NLO response,optical band gap and phase matching ability of complex coordinated NLO materials.
基金supported by the National Natural Science Foundation of China (22275131)the Institutional Research Fund from Sichuan University (2021SCUNL201)+1 种基金the 111 Project (B20001)the Fundamental Research Funds for the Central Universities。
文摘With the increase of people’s demand,it is extremely desired for developing high-safety,widetemperature-range and high-energy-density lithium batteries,but huge challenges are remained due to shrinkage and combustion of commonly used polyolefin separators at high temperatures,as well as narrow usable temperature range and high flammability of conventionally commercialized liquid electrolytes.In this work,we report a multifunctional separator mainly consisting of Zn^(2+)-phytate coordination complex nanoparticles and bacterial cellulose nanofibers,named the BZP separator,which possesses high porosity,excellent thermotolerance,good flame retardancy,abilities of anion binding and Ni^(2+)capturing.Through cooperating with the fluoride-free wide-temperature-range electrolyte,Li//LiFePO_(4) cells not only deliver discharge capacities of 110.39 mA h g^(-1)and 113.25 mA h g^(-1)after 2200 cycles (2 C) and1600 cycles (5 C) at 25℃,with capacity retentions of 76.59%and 86.09%,respectively,but also exhibit excellent cycling performance at 80℃ and-40℃.Significantly,the Li//NCM811 cell with a loading of7.8 mg cm^(-2)delivers a discharge capacity of 146.64 mA h g^(-1)after 200 cycles at 0.5 C,with a capacity retention of 89.03%.In addition,pouch cells can work at 120℃ and have low flammability.
基金supported by grant No.98U587 from Abadan University of Medical Sciences。
文摘Narrow solar-light response range and rapid charges recombination are the main technical barriers in TiO_(2) photocatalysis technology.To overcome these restrictions,in this work we synthesized a novel binuclear gadolinium(Ⅲ) coordination complex,[Gd_(2)(DPDB)_6(DMF)_6(H_(2)O_()2)](DPDB=[(4-dimethylamino)phenyldiazenyl] benzenesulfonate),which was used as an inorganic sensitizer for boosting the visible light-harvesting and quantum efficiency of TiO_(2) supported-reduced graphene oxide(rGO) nanocomposite.Crystal structure of [Gd_(2)(DPDB)_6(DMF)_6(H_(2)O)_(2)](Gd-CMP) was determined from single-crystal X-ray diffraction data,which indicates three-dimensional(3D) supramolecular architecture through hydrogen bonding and CH…π_(ph) interactions.The prepared nanohybrid(Gd-CMP/TG) reveals significantly enhanced visible-light-induced photocatalytic activity for degradation of acetaminophen(ACT).The complete removal of 10 mg/L ACT is achieved over Gd-CMP/TG,and the corresponding rate constant of ACT degradation of nanohybrid is 40-fold higher than that of bare TiO_(2).In prepared ternary nanohybrid,metal-coordination sensitizer(Gd-CMP) acts as an electron donor,and at the same time,rGO serves as an electron acceptor,and the synergistic effect between them efficiently enhances charges separation and inhibits e/h pair recombination in the hybridized species.The radical scavenger tests indicate that the photo-induced O_(2)^(-·) radicals dominate ACT degradation.On the basis of the experimental results and calculated energy of electronic levels,a possible mechanism for the improved photocatalytic activity is discussed.
基金the National Natural Science Foundation of China(U1910202,21978194 and 21603256)the Natural Science Foundation of Shanxi Province(201801D121055)Program for the Shanxi Young Sanjin Scholar.
文摘With the development of coal chemical industry,large amounts of naphthalene and n-butene are produced,and converting them into high value-added products through alkylation has gained particular importance and interest.In this work,liquid coordination complexes(LCCs)were used as acid catalysts for the first time in the naphthalene alkylation reaction under mild conditions to obtain multibutylnaphthalenes with high yield.Various reaction conditions were thoroughly investigated.The LCC consisting of urea and AlCl_(3) showed excellent catalytic performance under optimal reaction conditions,giving 100%conversion of naphthalene and 99.66%selectivity towards multi-butylnaphthalenes.Combining the catalyst properties and catalytic results,a plausible reaction mechanism was proposed.The lubricating properties of the synthesized products were investigated for their potential application as lubricating base oils.The synthesized multi-butylnaphthalenes showed comparable physicochemical properties and tribological performances as the commercial cycloalkyl base oil.
基金Project supported by the Nonprofit Technology & Research in Zhejiang (2011C37010)sponsored by the K.C.Wong Magna Fund in Ningbo University, the Ningbo Municipal Natural Science Foundation (2010A610160),the Subject Object (xk1070) and Foundation (20111045) of Ningbo University
文摘Two 1D coordination polymers [Ln2（dpdc）3（tpy）2·H2O]n [Ln=Nd 1, Yb 2, H2dpdc=2,2＇-biphenyldicarboxylic acid and tpy= 2,2＇：6＇,2＇＇-terpyridine] and one dinuclear complex Er2（dpdc）2（Hdpdc）2（tpy）2 3 were obtained via hydrothermal reactions and determined by X-ray diffraction analysis. The crystal structure data of 1 and 2 revealed that two coordination polymers were isostructural and possessed a 1D chain framework consisting of eight-coordinated Ln（III） centers. In the asymmetric unit, the two Er（III） ions in 3 were both nine-coordinated and had similar coordination environments. The Er（III） ions were bridged by dpdc2-ligands into dinuclear structures. The complexes were also characterized by IR spectra and thermogravimetric analysis. The solid fluorescence of 1 and 3 was also investigated at room temperature.
基金the Hunan Provincial Educational Ministry Foundation of China(00C001)
文摘Two coordinate reactions,NdCl 3·6H 2O(s)+3CCl 3COOH(s)(or TCA)=Nd(TCA)3·3H 2O(s)+3HCl(g)+3H 2O(l)and Nd(TCA)3·3H 2O(s)+2C 9H 7NO(s)=Nd(TCA)(C 9H 6NO)2(s)+2CCl 3COOH(s)+3H 2O(l),were studied by the classical solution calorimetry at 298.15K.The molar dissolution enthalpies of the reactants and the products in certain solvent(the first reaction in 1 mol·L-1 HCl,the second in a mixed solution consisting of absolute ethyl alcohol,dimethyl sulfoxide and 4 mol·L-1 HCl)were measured by using an isoperibol calorimeter at 298.15K.From the results and other auxiliary quantities,the standard molar formation enthalpies of[Nd(TCA)3·3H 2O,s,298.15K]and[Nd(TCA)(C 9H 6NO)2,s,298.15K]are determined asΔfH m°[Nd(TCA)3·3H 2O,s,298.15K]=-3053.3 kJ·mol-1 andΔfH m°[Nd(TCA)(C 9H 6NO)2,s,298.15K]=-1355.6 kJ·mol-1.
基金Supported by the National Natural Science Foundation of China(No.21301069)the Natural Science Foundation of Shandong Province(No.ZR2012BQ004)
文摘A new coordination complex [Cd(pda)(pyz)(H2O)2]n(1, H2 pda = 1,4-phenylenediacetic acid, pyz = pyrazine) have been synthesized and structurally characterized. Crystal data for the title complex are as follows: orthorhombic system, space group Ccmb with a = 11.5245(3) b = 19.5069(5) c = 11.4231(3) A, V = 2568.00(12) A3, Mr = 188.31, Z = 16, F(000) = 1480, Dc = 1.948 g/cm3, μ(Mo Kα) = 1.725 mm-1, R = 0.0195 and w R = 0.0462 for 1357 observed reflections with I 】 2σ(I). In the title complex, the central Cd(II) ion is located in a distorted octahedral coordination environment. Two Cd(II) ions are bridged by two pda2- ligands and one pyz ligand to form a bi-loop structure. Luminescent property of the complex has also been studied.
基金the National Natural Science Foundation of China (20425313)the Natural Science Foundation of Fujian Province (2005HZ01-1, 2006L2005, 2006F3135, 2006J0183)
文摘The reactions of Co（C1O4）2·6H2O and Co（NO3）2.6H2O with the di-Schiff base ligand N,N＇-bis-（1-benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine （LA） in ethanol have been investigated. The reactions of LA with excess amount of cobalt salts yield the six-coordinate complexes [CoL2]（ClO4）E·H2O 1 and [CoL2]（NO3）E·H2O 2 as isolatable products （L= N-（1- benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine）, where L is a tri-dentate mono-Schiff base ligand, resulting from the hydrolysis of the precursor di-Schiff base LA. Both complexes were characterized by X-ray crystallography. Crystal data for complex 1： monoclinic, space group P21/c, a = 11.9214（10）, b = 23.5828（17）, c = 14.0387（12）A, β = 135.219（4）°, C22H30Cl2CoN8O9, Mr = 680.37, V = 2780.1（4） A^3 ,Z = 4, Dc = 1.625 g/cm^3,μ（MoKa） = 0.876 mm^-1, F（000） = 1404, the final R = 0.0725 and wR = 0.1530 for 5726 observed reflections （I 〉 2σ（I））. Crystal data for complex 2： monoclinic, space group P21/c, a = 18.2162（16）, b = 10.0610（6）, c = 18.593（2）A, β = 130.099（3）°, C22H30CoN10O7, Mr = 605.49, V = 2606.5（4） A3 Z = 4, Dc = 1.543 g/cm^3,μ（MoKa） = 0.722 mm^-1, F（000） = 1260, the final R = 0.0619 and wR = 0.1429 for 5194 observed reflections （I 〉 2σ（I））. X-ray diffraction analysis reveals that each cobalt atom in the two complexes is chelated by six nitrogen atoms from two tridentate iigands L, exhibiting a slightly distorted octahedral coordination sphere. In both complexes, the strong hydrogen-bonding interactions between the lattice waters and N-H groups of the ligands result in 1D chains which are further connected by ClO4^- （or NO3^-） groups to form a 3D framework. In complex 2, the strong π-π interactions increase the stability of the structure.
基金supported by the National Basic Research Program of China (No. 2013CB934200)National Basic Research Program of China (No. 2012CB933001)+1 种基金The Chinese Academy of Sciences (No. YZ201318)the National Natural Science Foundation of China (Nos. 21472029, 51173031, 91127043, 51203030, 51463002)
文摘The formation of coordinated dimeric complexes bridged by axial ligands on surface is observed with the help of a 1,3,5-tris（10-carboxydecyloxy）benzene（TCDB） template through scanning tunneling microscopy（STM）. STM images of molecular adlayers of zinc tetraphenylporphyrin（Zn TPP）, zinc phthalocyanine（Zn Pc）, and their mixture are reported. Zn TPP and Zn Pc can spontaneously form highly an ordered structure with a 1：1 molar ratio, which is different from that of individual Zn Pc. The coordinated bimolecular complexes bridged with axial ligands, simply as Zn Pc–DPP–Zn TPP and Zn Pc–DPE–Zn Pc, are presented and the corresponding surface structures are compared. Zn Pc and Zn TPP can be connected by an axial ligand DPP and formed assembled structures out of surface. Two types of arrays with entirely new structure are obtained for the Zn Pc–DPE–Zn Pc complex. These bridged hybrid complexes provide an example of design of self-organized crystals on the basis of coordination through non-covalent interactions.
基金supported by the National Natural Science Foundation of China (No. 21407021)the Shanghai Yang-Fan Program of Science and Technology Commission of Shanghai (No. 14YF1405000)+1 种基金the National Key Research and Development Program of China (No. 2016YFC0400501)the Fundamental Research Funds for the Central Universities and DHU Distinguished Young Professor Program
文摘Chitosan–metal complexes have been widely studied in wastewater treatment, but there are still various factors in complex preparation which are collectively responsible for improving the adsorption capacity need to be further studied. Thus, this study investigates the factors affecting the adsorption ability of chitosan–metal complex adsorbents, including various kinds of metal centers, different metal salts and crosslinking degree. The results show that the chitosan–Fe（ Ⅲ） complex prepared by sulfate salts exhibited the best adsorption efficiency（100%） for various dyes in very short time duration（10 min）, and its maximum adsorption capacity achieved 349.22 mg/g. The anion of the metal salt which was used in preparation played an important role to enhance the adsorption ability of chitosan–metal complex. SO4^（2-） ions not only had the effect of crosslinking through electrostatic interaction with amine group of chitosan polymer, but also could facilitate the chelation of metal ions with chitosan polymer during the synthesis process.Additionally, the p H sensitivity and the sensitivity of ionic environment for chitosan–metal complex were analyzed. We hope that these factors affecting the adsorption of the chitosan–metal complex can help not only in optimizing its use but also in designing new chitosan–metal based complexes.
基金Supported by the National Natural Science Foundation of China(21401024)Natural Science Foundation of Anhui Province(1508085MB21)+3 种基金Key Project of Natural Science Research in Universities of Anhui Province(KJ2016A550)Major Scientific and Technological Achievements Incubation Fund Project of Fuyang Normal College(kjfh201606)National Students Research Training Program(201510371013,201610371015)Doctoral Startup Foundation of Fuyang Normal College(FSB201501010)
文摘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.
基金Project supported by the National Natural Science Foundation of China (Grant No 10774103)the Doctoral Education Fund of the Education Ministry of China (Grant No 20050610011)
文摘By simulating the electron paramagnetic resonance （EPR） and optical spectra on the basis of the 120 × 120 complete energy matrix, this paper determines the local lattice structure parameters R1 and R2 for MCl：V2＋ （M=Na, K, Rb） systems at 77K, 195 K and RT （room temperature 295 K or 302 K）, respectively. The theoretical results indicate that there exists a compressed distortion in MCl：V2＋ systems. Meanwhile, it finds that the structure parameters R1, R2 and ｜△R｜（ = R1 - R2） increase with the rising temperature. Subsequently, from the analysis it concludes that the relation of EPR parameter D vs. △R is approximately linear. Finally, the effects of orbital reduction factor k on the g factors for the three systems have been discussed.
基金Supported by the Natural Science Foundation of Anhui Province (090416239)the Science and Technology Play (?) Projects of Anhui Province (09020203071)+2 种基金the National Natural Science Foundation of China (20871089)the Foundation of Anhui Provincial Education Department for Outstanding Young Talents in University (2009SQRZ172)the Scientific Research Foundation for the Professors (Doctors) of Suzhou University (2010jb01)
文摘Two new transition metal compounds, [Mn（dpa）2（tmd）2]n （1, H2dpa = 4-hydroxy-phenyl-acetic acid, tmd = 4,4-trimethylenedipyridine） and [Co4（dpa）6（tmd）4（H2O）4]n·nH2O·nCl2 （2）, have been synthesized by hydrothermal synthesis. Compound 1 crystallizes in the monoclinic system, space group P21/n with a = 9.828（3）, b = 17.493（5）, c = 11.616（4）, β = 110.146（6）o, V = 1874.9（10）3, C42H42MnN4O6, Mr = 753.74, Z = 2, Dc = 1.335 g/cm3, μ = 0.406 mm-1, F（000） = 790, the final R = 0.1047 and wR = 0.2021 for 2698 observed reflections （I 〉 2σ（I））. Compound 2 crystallizes in the monoclinic system, space group P21/c with a = 11.7214（13）, b = 17.1582（19）, c = 24.625（3）, β = 103.055（3）o, V = 4824.4（9）3, C100H104Cl2Co4N8O23, Mr = 2094.55, Z = 2, Dc = 1.443 g/cm3, μ = 0.809 mm-1, F（000） = 2180, the final R = 0.0550 and wR = 0.0673 for 4104 observed reflections （I 〉 2σ（I））. These complexes were characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. The structural analyses show that the two compounds are both one-dimensional chain structures. However, compounds 1 and 2 form threedimensional supramolecular structures by hydrogen bonds, respectively.
基金Supported by the Key projects of Hubei Provincial Education Department(D20171902)
文摘Two new cobalt（II） coordination complexes, namely [Co（HL）2（biim）（H2O）2]n·n H2O（1） and [Co（Et L）2（biim）]n·3 n（H2O）·2 n（Et HL）（2）（H2L =（fluorene-9,9-diyl）dipropanoic acid, biim = 1,3-bis（imidazol-1-yl）butane）, have been synthesized using the same starting reactants but different solvent medium. The two complexes exhibit distinctly different structures. Compound 1 exhibits a one-dimensional linear chain structure. However, complex 2 reveals a one-dimensional zigzag chain structure. Thermogravimetric analyses（TGA） and luminescent properties of these two complexes have been discussed.
基金Supported by the National Natural Science Foundation of China (No.20671064)Doctor Foundation of Liaoning Province (No.20071016)
文摘The 1-D chain coordination complex of {[Mn2（HCAM）3（H2bipy）]·5H2O}n （H3CAM = 4-hydroxypyridine-2,6-dicarboxylic acid, bipy = 4,4＇-bipyridine） has been synthesized by the reaction of 4-hydroxypyridine-2,6-dicarboxylic acid, 4,4＇-bipyridine and manganese carbonate under hydrothermal conditions, and its crystal structure was determined by X-ray diffraction method The crystal belongs to the monoclinic system, space group P21/n with a = 10.110（2）, b = 20.159（4）, c = 17.861（4）A,β = 99.67（3）°, V = 3.5884（12） nm3, Mr= 901.47, Z = 4, Dc= 1.669 g.cm^-3, μ= 0.798 mm^-1, F（000） = 1840, the final R = 0.0713 and ωR = 0.1853. The complex forms a 1-D chain bridged by HCAM, protonated 4,4-bipyridines link the 1-D chains to construct 2-D networks via N-H...O hydrogen bonds, and networks are further extended via π-π stacking and hydrogen bonds into 3-D supramolecular framework.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.91636216,11974382,and 11474316)the Chinese Academy of Sciences Strategic Priority Research Program(Grant No.XDB21020200)+1 种基金by the YIPA Programthe support of NSERC,SHARCnet,ACEnet of Canada。
文摘In atomic,molecular,and nuclear physics,the method of complex coordinate rotation is a widely used theoretical tool for studying resonant states.Here,we propose a novel implementation of this method based on the gradient optimization(CCR-GO).The main strength of the CCR-GO method is that it does not require manual adjustment of optimization parameters in the wave function;instead,a mathematically well-defined optimization path can be followed.Our method is proven to be very efficient in searching resonant positions and widths over a variety of few-body atomic systems,and can significantly improve the accuracy of the results.As a special case,the CCR-GO method is equally capable of dealing with bound-state problems with high accuracy,which is traditionally achieved through the usual extreme conditions of energy itself.
文摘The ligand o-phenylenediamine (opda) and its oxidized form, o-benzoquinonediimine (bqdi), act as a fascinating candidate coordinating toward transition metal ions leading to the photochemical hydrogen production in absence of photosensitizers. Herein, we report the systematic study of the interaction between the oxidized form bqdi ligand, tris-(o-benzoquinonediimine) with divalent first-row transition metal series using DFT calculations. The lowest energy structures, bond length, binding energies, frontier molecular orbital analysis, natural bond orbitals, and global reactivity descriptor were calculated using B3LYP/6-311G(d,P) level of theory. The time dependent-DFT at the CAM-B3LYP/6-311+G(d,p) level of theory was applied to determine the electronic structures and the optical spectra. The theoretical binding trend of the divalent first-row transition metal series is decreasing as follows: Cu >Ti > V > Co > Ni > Fe > Cr > Zn >Mn. Among them, the binding potency of iron (II) by the bqdi ligand was not predominantly sturdy as compared to other first-row divalent transition metal ions. The origin of strong coordination with Fe(II) is attributed to its extra capability to induce covalent coordination of bqdi ligands. The complex exhibited two strong peaks at 370 nm and 452 nm, due to the HOMO-3 to LUMO+1 and HOMO-1 to LUMO transitions, respectively. Natural bond orbital analysis showed that the major interaction happens between the N lone pair electrons of the ligand with an anti-bonding orbital of metal ions, in which Ti showed the highest interaction energy than other metal ions. The present systemic DFT study of bqdi ligands with the first-row transition metals strongly encourages the future establishment of photochemical hydrogen production in absence of photosensitizers.
基金supported by the National Natural Science Foundation of China(21373221)the Natural Science Foundation of Fujian Province(2006L2005 and 2014H0007)
文摘A novel coordination complex,{[Cd）2（C（20）H（10）O5）2（H2O）4]·10H2O}n,has been synthesized based on fluorescein（2-（6-hydroxy-3-oxo-3 H-xanthen-9-yl） benzoic acid） and systematically characterized by elemental analysis,infrared（IR） spectrum,thermo gravimetric analysis（TGA）,powder X-ray diffraction（PXRD） and single-crystal X-ray diffraction.Compound 1 crystallizes in monoclinic,space group P2/n with a = 20.428（5）,b = 8.084（2）,c = 21.689（5）A,β = 96.360（5）°,Mr = 993.46,V = 3559.7（15）A^3,Z = 4,Dx = 1.845 g/cm^3,μ = 1.276 mm^-1,F（000） = 1974,GOOF = 1.044,λ（Mo Kα） = 0.71073 ？,the final R = 0.0553 and wR = 0.1720 for 7245 observed reflections with I 〉 2σ（I）.
基金Supported by NNSFC(Nos.21271121,21471092,21571118)
文摘The reaction of the reduced Schiff base HL（N-（4-hydroxybenzyl）-L-serine） with Zn（CH3COO）2·2H2O in aqueous solution afforded [Zn（L）2]·3H2O（I）. The complex has been characterized by elemental analysis, FT-IR, powder X-ray diffraction, electrospray ionization mass spectrometry and single-crystal X-ray diffraction. Complex I crystallizes in the orthorhombic system, space group P212121, with a=9.197（2）, b=10.445（2）, c=24.149（5） , V=2319.8（8） 3, Z=4, C（20）H（30）N2O11 Zn, Mr=539.83, Dc=1.546 g·cm3, μ=1.122 mm（-1）, F（000）=1128, GOOF=0.971, the final R=0.0206 and w R=0.0506 for 4346 observed reflections（I ＆gt; 2σ（I））. In complex I, each Zn（II） ion coordinates with three carboxyl oxygen atoms and two amine nitrogen atoms from three L-anions, forming a distorted five-coordinated trigonal bipyramidal geometry. Complex I exhibits a 1D wavy chain structure that is extended by hydrogen-bonding interactions to form a supramolecular network. The bioactivity of the complex as a potential PTPs inhibitor in vitro was investigated, displaying potent inhibition against PTP1B（IC（50）, 0.24 μM） and TCPTP（IC（50）, 0.53 μM） with a moderate selectivity.
基金the support of National Science Foundations of China(No.21461001)the Project of Jiangxi Provincial Department of Education(Nos.GJJ170436 and GJJ180367)+1 种基金the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.19JKB150007)the Doctoral Scientific Research Foundation of East China University of Technology(No.DHBK2019143)。
文摘Two new hydrostable two-dimensional(2 D)uranyl coordination complexes[(UO_(2))_(5)(μ_(3)-O)_(2)(nbca)_(2)].7 H_(2)O(1)and[(UO_(2))_(3)(nbca)_(2)(H_(2)O)_(3)]·2 H_(2)O(2)(H_(3)nbca=5-nitro-1,2,3-benzenetricarboxylic acid)were hydrothermal synthesized.Single-crystal structural refinements reveal that both of the two complexes were formed by the packing of 2D uranyl coordination sheets via the hydrogen bonds.The nbca ligand coordinating to the uranyl polyhedron centers constructed the 2D sheets.There are UO8 hexagonal bipyramids and UO7 pentagonal bipyramids in 1 while only U07 pentagonal bipyramids in 2.Photocatalytic degradation of rhodamine B(RhB)in aqueous solution was studied.Complex 2 possesses better performance than 1 with 96.2%of the RhB was degraded in only 60 min.Mechanism studies reveal that the dissolved oxygens are essential to the RhB degradation.The photocurrent density of 2 is more stable than that of 1,which indicating the stronger ability to separate photoexcited electrons and hole pairs of 2.
