Selective oxidation of olefin to epoxides is an important reaction in industry,however,developing heterogeneous catalysts to achieve the effective catalysis for this reaction under O_(2)atmosphere at room temperature ...Selective oxidation of olefin to epoxides is an important reaction in industry,however,developing heterogeneous catalysts to achieve the effective catalysis for this reaction under O_(2)atmosphere at room temperature is challenging but highly desired.In this work,two novel 2D cobalt metal-organic complexes,namely[Co(L)(5-HIP)]·2H_(2)O(Co-MOC-1)and[Co(L)(BTEC)_(0.5)]·H_(2)O(Co-MOC-2)(L=(E)-4,4-(ethene-1,2-diyl))bis(N-(pyridin-3-yl)benzamide;5-H_(2)HIP=5-hydroxyisophthalic acid;H4BTEC=pyromellitic acid)were designed and synthesized through hydrothermal method,which exhibited different metal coordination modes(4-coordinate and 5-coordinate,respectively)and 2D layer structures directed by different carboxylates co-ligands.Two Co-MOCs can serve as heterogeneous catalysts for the selective oxidation of olefins to epoxides at room temperature using O_(2)as oxidant.Furthermore,a higher catalysis activity of Co-MOC-1 than Co-MOC-2(96.7%vs.90.2%yield of 1,2-epoxycyclooctane)was observed,which may be attributed to the coordination unsaturated Co centers,the less coordination number and larger interlayer spacing of Co-MOC-1.展开更多
Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex...Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex[Pt(κ^(3)-N^C^N')(CNXyl)]Cl([A]Cl)and the molecular complex[Pt(κ^(2)-N^C^N')(CNXyl)Cl](B).Isomer B was almost the dominating product.The structures of the isomer B derivatives bearing-CF_(3)and-Cl substituents on the pyridine ring of the pinene moiety(5B and 7B,respectively)have been confirmed by single-crystal X-ray diffraction,revealing a slightly distorted square planar geometry with trans-N_(N^C^N'),CNR configuration(The terminal N atom of theκ^(2)-N^C^N'ligand is trans to the isocyanide ligand CNXyl.).Isomer B is thermodynamically more stable,as confirmed by theoretical calculations.CCDC:2416415,5B;2416414,7B.展开更多
Tetraphenylethylene(TPE) and its derivatives, as the widely used aggregation-induced emission(AIE) fluorophores, have attracted rapidly growing interest in the fields of material science and biological technology due ...Tetraphenylethylene(TPE) and its derivatives, as the widely used aggregation-induced emission(AIE) fluorophores, have attracted rapidly growing interest in the fields of material science and biological technology due to their unique light-emitting mechanism—they are nearly non-emissive in dilute solution but emit brilliant fluorescence in the aggregate state because of the restriction of intramolecular motion. Coordination-driven self-assembly, which provides a highly effective method to put the individual chromophores together, is consistent with the AIE mechanism of TPE. During the past few years, some AIE-active metal-organic coordination complexes have been successfully constructed via coordination-driven self-assembly, and their AIE properties and applications have been investigated. In this review, we survey the recent progress on TPE-based metal-organic coordination complexes and their applications in fluorescence sensors, cell imaging, and light-emitting materials. We will introduce them from three different types of structures: metallacycles, metallacages, and metal-organic frameworks(MOFs).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
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 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
Three complexes obtained by the reaction of Pr（Ⅲ） or Nd（Ⅲ） salts with 5-methyl-2-pyrazinecarboxylic acid（Hmpca） are structurally determined by single-crystal X-ray diffraction.Complex [Pr（mpca-）3（H2O）2]2&#...Three complexes obtained by the reaction of Pr（Ⅲ） or Nd（Ⅲ） salts with 5-methyl-2-pyrazinecarboxylic acid（Hmpca） are structurally determined by single-crystal X-ray diffraction.Complex [Pr（mpca-）3（H2O）2]2·6H2O（1） is composed of dinuclear Pr（Ⅲ） units with two metal centers bridged by two anionic mpca-ligands in a κ^3O,O＇：O＇ bridging mode.Complexes [Pr（mpca-）3]n（2） and [Nd（mpca-）3]n（3） are isostructures,and they consist of polymeric chains based on Ln（Ⅲ） and mpca-ligands.Each pair of adjacent metal centers is linked by three mpca-molecules in a κ^3N,O：O bridging mode.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
<span style="font-family:Verdana;">Coordination compounds of 2-amino-3-methylbutanoic acid were synthesized with chromium(III) and oxovanadium(IV) ions. M:L;1:2. Adducts of these complexes using 1,10-p...<span style="font-family:Verdana;">Coordination compounds of 2-amino-3-methylbutanoic acid were synthesized with chromium(III) and oxovanadium(IV) ions. M:L;1:2. Adducts of these complexes using 1,10-phenantroline and ethylenediamine were further synthesized, M:L, (1:2). These compounds were characterized using electronic, infra-red spectrophotometry, magnetic susceptibility measurement and percentage metal analyses. The zones of inhibition and minimum inhibitory concentrations of the compounds against eight microbes were studied. The results obtained indicated an octahedral geometry for the Cr(III) complexes, indicative of additional coordination of two water molecules. On the other hand a square pyramid geometry was obtained for the binary oxovanadium complex and its 1,10-phenantroline adduct. However</span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">,</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;"> for the oxovanadium ethylenediamine adduct a distorted octahedral geometry was proposed. The result for the antibacterial studies indicated that both mixed ligand complexes of 1,10-phenantroline exhibited good antibacterial activity, and in some cases better activity than the standard, streptomycin.</span></span></span>展开更多
<span style="font-family:Verdana;">Coordination compounds of 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="fo...<span style="font-family:Verdana;">Coordination compounds of 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one with </span><span style="font-family:Verdana;">iron(III), cobat(III) and chromium(III) were synthesized with M:L (1:2)</span><span style="font-family:Verdana;">. Mixed ligand coordination compounds of 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one and 1,2-diaminocyclohexane using the same metal ions were also synthesized </span><b><span style="font-family:Verdana;">M:L1</span></b><span style="font-family:Verdana;">:</span><b><span style="font-family:Verdana;">L2</span></b><span style="font-family:Verdana;"> (1:1:1) where </span><b><span style="font-family:Verdana;">L1</span></b><span style="font-family:Verdana;"> is 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one and </span><b><span style="font-family:Verdana;">L2</span></b><span style="font-family:Verdana;"> is 1,2-diaminocyclohexane. The coordination compounds obtained were characterized using electronic and infrared spectral analyses, magnetic susceptibility and percentage metal analysis. They were also evaluated for their cytotoxic and antioxidant activities. The result obtained suggested that octahedral geometry was obtained for all the compounds, as a result of additional two molecules of the solvent coordinated to the metal ions. Both the primary and secondary ligands coordinated in a bidentate fashion. The synthesized compounds exhibited moderate cytotoxicity, although none was as active as the standard. The cobalt(III) mixed ligand complex elicited the highest activity. The synthesized compounds all exhibited good to moderate antioxidant activity.</span>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
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
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
Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfull...Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy,elemental analyses,single-crystal X-ray diffraction,powder X-ray diffraction,and thermogravimetric analysis.The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.Meanwhile,complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.In addition,both 1and 2 exhibited luminescent properties in the solid state.Furthermore,quantum chemical calculations were carried out on the"molecular fragments"extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian 16 program.The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ)ions.CCDC:2332173,1;2332176,2.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
To analyze and control complex networks effectively, this paper puts forward a new kind of scheme, which takes control separately in each area and can achieve the network’s coordinated optimality. The proposed algori...To analyze and control complex networks effectively, this paper puts forward a new kind of scheme, which takes control separately in each area and can achieve the network’s coordinated optimality. The proposed algorithm is made up of two parts: the first part decomposes the network into several independent areas based on community structure and decouples the information flow and control power among areas; the second part selects the center nodes from each area with the help of the control centrality index. As long as the status of center nodes is kept on a satisfactory level in each area, the whole system is under effective control. Finally, the algorithm is applied to power grids, and the simulations prove its effectiveness.展开更多
Four new five-coordinated anionic tin(Ⅳ) complexes with a form of [R_ n NH_ 4- n ][PhSn( μ 2-SCH_2COO)_2] were synthesized via the reaction of mercaptoacetic acid with phenyltin trichloride in the presence of dif...Four new five-coordinated anionic tin(Ⅳ) complexes with a form of [R_ n NH_ 4- n ][PhSn( μ 2-SCH_2COO)_2] were synthesized via the reaction of mercaptoacetic acid with phenyltin trichloride in the presence of different organic bases and characterized by means of IR, 1H NMR and MS spectroscopies. The crystal structure of [( i -Pr)_2NH_2] [PhSn( μ 2-SCH_2COO)_2] was determined by X-ray diffraction. In the crystal structure,the tin atom is five-coordinated and exists in trigonal bipyramid geometry with cell parameters a =1.1766(11) nm, b =1.3144(14) nm, c =1.3336(15) nm,β =90° and Z =4.展开更多
This study reveals that the noncovalent complexation betweenβ-CD and Cu（HMTA）^（2＋） makes a positive contribution to the coordination interaction between Cu^（2＋） and HMTA in a tricomponent system.Besides,mono-...This study reveals that the noncovalent complexation betweenβ-CD and Cu（HMTA）^（2＋） makes a positive contribution to the coordination interaction between Cu^（2＋） and HMTA in a tricomponent system.Besides,mono- and binuclear complexes：[β-CDCu]~＋ and[Cu·β-CDCu]~＋ were observed under the condition of ESI-MS.展开更多
Polyoxometalates（POMs） with Cd-coordination complexes acting as supporting units are rarely reported. The linkage of the supporting units with inorganic building block（polyanion） is generally established on termin...Polyoxometalates（POMs） with Cd-coordination complexes acting as supporting units are rarely reported. The linkage of the supporting units with inorganic building block（polyanion） is generally established on terminal O-atoms, but scarcely via bridging O-atoms. By introducing liquid small organic molecule（pyridine, C5NH5） as assistant ＂structure-directing agent＂, we obtained a novel organic-inorganic hybrid polytungstate,（Hpy）4[Cd（phen）2（P2W18O62）]·nH2O（1, n ≈ 3, py = pyridine, phen = 1,10-phenanthroline）, under hydrothermal conditions. The single-crystal X-ray diffraction analysis shows that 1 is the first compound containing an asymmetric heteropolyanion, [Cd（phen）2（P2W18O62）]4–, a Wells-Dawson-type polyanion monosupported by Cd-coordination complex via di-bridging O-atoms.展开更多
Fifteen M(S2COR)n complexes were prepared.According to the data provided by IR,UV-Vis absorption spectrometry and X-ray diffraction,this paper covers the relationship between molecular structures of xanthate complexes...Fifteen M(S2COR)n complexes were prepared.According to the data provided by IR,UV-Vis absorption spectrometry and X-ray diffraction,this paper covers the relationship between molecular structures of xanthate complexes and their absorption spectra and a criterion of chelate stability is also proposed.The stability mechanism of xanthate chelates and related rules were investigated.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.22271021,21971024,22201021)the Doctoral Scientific Research Foundation of Liaoning Province(No.2022-BS-302)。
文摘Selective oxidation of olefin to epoxides is an important reaction in industry,however,developing heterogeneous catalysts to achieve the effective catalysis for this reaction under O_(2)atmosphere at room temperature is challenging but highly desired.In this work,two novel 2D cobalt metal-organic complexes,namely[Co(L)(5-HIP)]·2H_(2)O(Co-MOC-1)and[Co(L)(BTEC)_(0.5)]·H_(2)O(Co-MOC-2)(L=(E)-4,4-(ethene-1,2-diyl))bis(N-(pyridin-3-yl)benzamide;5-H_(2)HIP=5-hydroxyisophthalic acid;H4BTEC=pyromellitic acid)were designed and synthesized through hydrothermal method,which exhibited different metal coordination modes(4-coordinate and 5-coordinate,respectively)and 2D layer structures directed by different carboxylates co-ligands.Two Co-MOCs can serve as heterogeneous catalysts for the selective oxidation of olefins to epoxides at room temperature using O_(2)as oxidant.Furthermore,a higher catalysis activity of Co-MOC-1 than Co-MOC-2(96.7%vs.90.2%yield of 1,2-epoxycyclooctane)was observed,which may be attributed to the coordination unsaturated Co centers,the less coordination number and larger interlayer spacing of Co-MOC-1.
文摘Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex[Pt(κ^(3)-N^C^N')(CNXyl)]Cl([A]Cl)and the molecular complex[Pt(κ^(2)-N^C^N')(CNXyl)Cl](B).Isomer B was almost the dominating product.The structures of the isomer B derivatives bearing-CF_(3)and-Cl substituents on the pyridine ring of the pinene moiety(5B and 7B,respectively)have been confirmed by single-crystal X-ray diffraction,revealing a slightly distorted square planar geometry with trans-N_(N^C^N'),CNR configuration(The terminal N atom of theκ^(2)-N^C^N'ligand is trans to the isocyanide ligand CNXyl.).Isomer B is thermodynamically more stable,as confirmed by theoretical calculations.CCDC:2416415,5B;2416414,7B.
基金financially supported by STCSM (No. 16XD 1401000)Program for Changjiang Scholars and Innovative Research Team in University
文摘Tetraphenylethylene(TPE) and its derivatives, as the widely used aggregation-induced emission(AIE) fluorophores, have attracted rapidly growing interest in the fields of material science and biological technology due to their unique light-emitting mechanism—they are nearly non-emissive in dilute solution but emit brilliant fluorescence in the aggregate state because of the restriction of intramolecular motion. Coordination-driven self-assembly, which provides a highly effective method to put the individual chromophores together, is consistent with the AIE mechanism of TPE. During the past few years, some AIE-active metal-organic coordination complexes have been successfully constructed via coordination-driven self-assembly, and their AIE properties and applications have been investigated. In this review, we survey the recent progress on TPE-based metal-organic coordination complexes and their applications in fluorescence sensors, cell imaging, and light-emitting materials. We will introduce them from three different types of structures: metallacycles, metallacages, and metal-organic frameworks(MOFs).
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 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 (Nos. 20971065,20771005)National Basic Research Program of China (2007CB925103)+1 种基金the Young Teachers Program of College in Anhui Province (2008jql138)the Natural Science Foundation of Anhui Province (090416239)
文摘Three complexes obtained by the reaction of Pr（Ⅲ） or Nd（Ⅲ） salts with 5-methyl-2-pyrazinecarboxylic acid（Hmpca） are structurally determined by single-crystal X-ray diffraction.Complex [Pr（mpca-）3（H2O）2]2·6H2O（1） is composed of dinuclear Pr（Ⅲ） units with two metal centers bridged by two anionic mpca-ligands in a κ^3O,O＇：O＇ bridging mode.Complexes [Pr（mpca-）3]n（2） and [Nd（mpca-）3]n（3） are isostructures,and they consist of polymeric chains based on Ln（Ⅲ） and mpca-ligands.Each pair of adjacent metal centers is linked by three mpca-molecules in a κ^3N,O：O bridging mode.
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.
文摘<span style="font-family:Verdana;">Coordination compounds of 2-amino-3-methylbutanoic acid were synthesized with chromium(III) and oxovanadium(IV) ions. M:L;1:2. Adducts of these complexes using 1,10-phenantroline and ethylenediamine were further synthesized, M:L, (1:2). These compounds were characterized using electronic, infra-red spectrophotometry, magnetic susceptibility measurement and percentage metal analyses. The zones of inhibition and minimum inhibitory concentrations of the compounds against eight microbes were studied. The results obtained indicated an octahedral geometry for the Cr(III) complexes, indicative of additional coordination of two water molecules. On the other hand a square pyramid geometry was obtained for the binary oxovanadium complex and its 1,10-phenantroline adduct. However</span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">,</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;"> for the oxovanadium ethylenediamine adduct a distorted octahedral geometry was proposed. The result for the antibacterial studies indicated that both mixed ligand complexes of 1,10-phenantroline exhibited good antibacterial activity, and in some cases better activity than the standard, streptomycin.</span></span></span>
文摘<span style="font-family:Verdana;">Coordination compounds of 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one with </span><span style="font-family:Verdana;">iron(III), cobat(III) and chromium(III) were synthesized with M:L (1:2)</span><span style="font-family:Verdana;">. Mixed ligand coordination compounds of 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one and 1,2-diaminocyclohexane using the same metal ions were also synthesized </span><b><span style="font-family:Verdana;">M:L1</span></b><span style="font-family:Verdana;">:</span><b><span style="font-family:Verdana;">L2</span></b><span style="font-family:Verdana;"> (1:1:1) where </span><b><span style="font-family:Verdana;">L1</span></b><span style="font-family:Verdana;"> is 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one and </span><b><span style="font-family:Verdana;">L2</span></b><span style="font-family:Verdana;"> is 1,2-diaminocyclohexane. The coordination compounds obtained were characterized using electronic and infrared spectral analyses, magnetic susceptibility and percentage metal analysis. They were also evaluated for their cytotoxic and antioxidant activities. The result obtained suggested that octahedral geometry was obtained for all the compounds, as a result of additional two molecules of the solvent coordinated to the metal ions. Both the primary and secondary ligands coordinated in a bidentate fashion. The synthesized compounds exhibited moderate cytotoxicity, although none was as active as the standard. The cobalt(III) mixed ligand complex elicited the highest activity. The synthesized compounds all exhibited good to moderate antioxidant activity.</span>
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 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.
文摘Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy,elemental analyses,single-crystal X-ray diffraction,powder X-ray diffraction,and thermogravimetric analysis.The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.Meanwhile,complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.In addition,both 1and 2 exhibited luminescent properties in the solid state.Furthermore,quantum chemical calculations were carried out on the"molecular fragments"extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian 16 program.The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ)ions.CCDC:2332173,1;2332176,2.
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the National Science Foundation of China (No.50525721, 50595411)the National Basic Research Program of China(No.G2004CB217902)
文摘To analyze and control complex networks effectively, this paper puts forward a new kind of scheme, which takes control separately in each area and can achieve the network’s coordinated optimality. The proposed algorithm is made up of two parts: the first part decomposes the network into several independent areas based on community structure and decouples the information flow and control power among areas; the second part selects the center nodes from each area with the help of the control centrality index. As long as the status of center nodes is kept on a satisfactory level in each area, the whole system is under effective control. Finally, the algorithm is applied to power grids, and the simulations prove its effectiveness.
文摘Four new five-coordinated anionic tin(Ⅳ) complexes with a form of [R_ n NH_ 4- n ][PhSn( μ 2-SCH_2COO)_2] were synthesized via the reaction of mercaptoacetic acid with phenyltin trichloride in the presence of different organic bases and characterized by means of IR, 1H NMR and MS spectroscopies. The crystal structure of [( i -Pr)_2NH_2] [PhSn( μ 2-SCH_2COO)_2] was determined by X-ray diffraction. In the crystal structure,the tin atom is five-coordinated and exists in trigonal bipyramid geometry with cell parameters a =1.1766(11) nm, b =1.3144(14) nm, c =1.3336(15) nm,β =90° and Z =4.
文摘This study reveals that the noncovalent complexation betweenβ-CD and Cu（HMTA）^（2＋） makes a positive contribution to the coordination interaction between Cu^（2＋） and HMTA in a tricomponent system.Besides,mono- and binuclear complexes：[β-CDCu]~＋ and[Cu·β-CDCu]~＋ were observed under the condition of ESI-MS.
基金supported by the Foundation of Education Department of Fujian Province(Nos.JB12199 and JA11245)the National Natural Science Foundation of China(Nos.21233004 and 40972035)
文摘Polyoxometalates（POMs） with Cd-coordination complexes acting as supporting units are rarely reported. The linkage of the supporting units with inorganic building block（polyanion） is generally established on terminal O-atoms, but scarcely via bridging O-atoms. By introducing liquid small organic molecule（pyridine, C5NH5） as assistant ＂structure-directing agent＂, we obtained a novel organic-inorganic hybrid polytungstate,（Hpy）4[Cd（phen）2（P2W18O62）]·nH2O（1, n ≈ 3, py = pyridine, phen = 1,10-phenanthroline）, under hydrothermal conditions. The single-crystal X-ray diffraction analysis shows that 1 is the first compound containing an asymmetric heteropolyanion, [Cd（phen）2（P2W18O62）]4–, a Wells-Dawson-type polyanion monosupported by Cd-coordination complex via di-bridging O-atoms.
文摘Fifteen M(S2COR)n complexes were prepared.According to the data provided by IR,UV-Vis absorption spectrometry and X-ray diffraction,this paper covers the relationship between molecular structures of xanthate complexes and their absorption spectra and a criterion of chelate stability is also proposed.The stability mechanism of xanthate chelates and related rules were investigated.
