Two new fluorinated phenylisoquinoline-based iridium（Ⅲ） complexes,[Ir（f2piq）2（bipy）][PF6]（3a） and[Ir（fmpiq）2（bipy）][PF6]（3b）（f2piq = l-（2,4-difluorophenyl）isoquinoline,fmpiq = 1-（4-fluoro-2-methylph...Two new fluorinated phenylisoquinoline-based iridium（Ⅲ） complexes,[Ir（f2piq）2（bipy）][PF6]（3a） and[Ir（fmpiq）2（bipy）][PF6]（3b）（f2piq = l-（2,4-difluorophenyl）isoquinoline,fmpiq = 1-（4-fluoro-2-methylphenyl）isoquinoline,bipy = 2,2＇-bipyridine）,have been synthesized and fully characterized.Single crystal X-ray diffraction study has been undertaken on complexes 3a and 3b,which show that each adopts the distorted octahedral coordination geometry with the cis-C,C＇ and trans-N,N＇ configuration.The photoluminescence spectra of 3a and 3b exhibit yellow and orange emission maxima at 584 and 600 nm,respectively.The frontier molecular orbital diagrams and the lowest-energy electronic transitions of 3a-3b have been calculated with density functional theory（DFT） and time-dependent DFT（TD-DFT）.The absorption and emission spectra of complex 3b is red-shifted relative to those of complex 3a,as a consequence of the nature of the methyl group.展开更多
The two complexes [HgI_2L]（DMF）（1） and [AgL_2]（ClO_4）（CH_3CN）（2） were synthesized from the reaction of Schiff base ligand（2-acetylpyridine-p-aminobenzoylhydrazone）（L） with HgI_2 or AgClO_4 respectively. ...The two complexes [HgI_2L]（DMF）（1） and [AgL_2]（ClO_4）（CH_3CN）（2） were synthesized from the reaction of Schiff base ligand（2-acetylpyridine-p-aminobenzoylhydrazone）（L） with HgI_2 or AgClO_4 respectively. The compounds are characterized by ^1H NMR,FTIR and elemental analysis. The structures of the ligand and two complexes are measured via single-crystal X-ray diffraction. In these two complexes,the structures are both distorted triangular bipyramids with five-coordinated centers.展开更多
A new stripping agent N,N-dimethyl-3-oxa-glutaramic Acid (DOGA) was used in TRPO process to simplify the TRPO process. The structures of the complexes of the DOGA with Eu(Ⅲ), Nd(Ⅲ), La(Ⅲ) were characterized with ex...A new stripping agent N,N-dimethyl-3-oxa-glutaramic Acid (DOGA) was used in TRPO process to simplify the TRPO process. The structures of the complexes of the DOGA with Eu(Ⅲ), Nd(Ⅲ), La(Ⅲ) were characterized with extended X-ray absorption fine structure spectroscopy (EXAFS), infrared spectra (IR) and mass spectra (MS). The molecular formula of the complexes of Eu(Ⅲ) and Nd(Ⅲ) is deduced to be M(DOGA)_3, and only La(Ⅲ) can form the complex HM(DOGA)_4 under condition of high consistency of the DOGA. The coordination number of Ln(Ⅲ) in the complexes is 8, and all of coordinated donor atoms are O atoms. For Eu(Ⅲ), Nd(Ⅲ), the coordination numbers of O atom in the first coordination shell is 6 and the average coordination bond lengths of Ln-O are 0 240 nm, 0 244 nm respectively, while the numbers of the second O shell are 2.4, and the average coordination bond lengths of Ln-O are 0 260 nm, 0 262 nm. For La(Ⅲ), the coordination numbers of O atom in the first coordination shell is 6 and the average coordination bond lengths of La-O are 0 258 nm, while the number of O atom in the second coordination shell is 4.4, and the average coordination bond length of La-O is 0 28 nm. The results of IR and MS show that there is no water coordinating with Ln(Ⅲ) in the complexes.展开更多
A new kind of Schiff base HL（HL= 1-phenyl-3-methyl-4-（p-methylbenzoyl）-5-pyrazolone with L-Leucine methyl ester） and complexes Ni L′_2·0.75C_2H_5OH·0.25H_2O,Cu L′′2（L′ = 1-phenyl-3-methyl-4-（p-meth...A new kind of Schiff base HL（HL= 1-phenyl-3-methyl-4-（p-methylbenzoyl）-5-pyrazolone with L-Leucine methyl ester） and complexes Ni L′_2·0.75C_2H_5OH·0.25H_2O,Cu L′′2（L′ = 1-phenyl-3-methyl-4-（p-methylbenzoyl）-5-pyrazolone with L-leucine ethyl,L′′ = 1-phenyl-3-methyl-4-（p-methylbenzoyl）-5-pyrazolone with L-leucine） have been synthesized and structurally determined by X-ray diffraction. For HL： crystal structure determination indicates that there are two independent HLs with different conformations in one asymmetric unit. For complex 1： the Ni（Ⅱ） ion is six-coordinated by two carbonyl oxygen atoms from pyrazolone ring,two nitrogen atoms from different HL′ and two oxygen atoms from L-Leucine ethyl ester to form a distorted octahedral geometry. For complex 2： the Cu（Ⅱ） ion is four-coordinated by one carbonyl oxygen atom from the pyrazolone ring,one nitrogen atom from HL′′,and two different carboxylic oxygen atoms from L-leucine with the same conformation to form a distorted quadrilateral geometry.展开更多
The functionalized calix[4]pyrrole meso-substituted Schiff bases were conveniently prepared by four- step synthetic route. Furthermore, the nickel and copper complexes of calix[4]pyrrole meso-substituted Schiff base w...The functionalized calix[4]pyrrole meso-substituted Schiff bases were conveniently prepared by four- step synthetic route. Furthermore, the nickel and copper complexes of calix[4]pyrrole meso-substituted Schiff base with 1：2 stoichiometry were obtained. The crystal structures of the calix[4]pyrroles and their metal complexes were determined by X-ray diffraction.展开更多
Two new complexes [Ag（bix）]n·n NAA·n H2O（1） and [Cd（NAA）（phen）2（H2O）]2· 2CH3COO-·H2O（2）（bix = 1,4-bis（imidazol-1-ylmethyl）benzene,HNAA = α-naphthylacetic acid,phen = 1,10-phenanthro...Two new complexes [Ag（bix）]n·n NAA·n H2O（1） and [Cd（NAA）（phen）2（H2O）]2· 2CH3COO-·H2O（2）（bix = 1,4-bis（imidazol-1-ylmethyl）benzene,HNAA = α-naphthylacetic acid,phen = 1,10-phenanthroline） have been successfully synthesized under hydrothermal conditions.Their structures have been determined by elemental analyses,IR spectroscopy,TG and single-crystal X-ray diffraction analysis.The intermolecular hydrogen bonding or π-π stacking interactions extend the complexes into a 3D supramolecular structure.Moreover,the luminescent properties of complex 2 have been investigated in the solid state.展开更多
Reaction of ferrocenoyl chloride with [Et;NH] [（μ-CO）(μ-RS) Fe;=（CO）;] complexes gave bridging ferrocenoyl complexes（μ-FcCO）(μ-RS)Fe;（CO）;（Fc=ferrocenyl, R=Et, i-Pr, n-Bu, t-Bu, Ph）.The structures of all...Reaction of ferrocenoyl chloride with [Et;NH] [（μ-CO）(μ-RS) Fe;=（CO）;] complexes gave bridging ferrocenoyl complexes（μ-FcCO）(μ-RS)Fe;（CO）;（Fc=ferrocenyl, R=Et, i-Pr, n-Bu, t-Bu, Ph）.The structures of all new complexes were characterised by;HNMR, IR and MS.展开更多
The two title complexes, [Cd{3,5-（NO2）2sal}（2,2′-bipy）]n 1 and [Mn{3,5- （NO2）2sal}（2,2′-bipy）]n 2 （3,5-（NO2）2sal = 3,5-dinitrosalicylate, 2,2＇-bipy = 2,2′-bipyridine）, were synthesized by the hydrother...The two title complexes, [Cd{3,5-（NO2）2sal}（2,2′-bipy）]n 1 and [Mn{3,5- （NO2）2sal}（2,2′-bipy）]n 2 （3,5-（NO2）2sal = 3,5-dinitrosalicylate, 2,2＇-bipy = 2,2′-bipyridine）, were synthesized by the hydrothermal reaction and structurally characterized. Complex 1 crystallizes in triclinic, space group P1, a = 5.581（4）, b = 12.071（8）, c = 12.88（1）A, α= 92.10（3）,β= 96.73（3）, γ = 102.02（2）°, C17H10N407Cd, Mr = 494.69, V= 841（1）A3, Z = 2, Dc = 1.954 g/cm3, F（000） = 488, μ= 1.353 mm^-1, R = 0.0248 and wR = 0.0761. Complex 2 crystallizes in monoclinic with space group P21/c, a = 8.604（3）, b = 23.88（1）, c = 8.894（3） A, β = 102.45（1）°, C17H10N407Mn, Mr = 437.23, V= 1785（1） A3, Z=.4, Dc = 1.627 g/cm3, F（000） = 884, μ = 0.791 mm^-1, R = 0.0471 and wR = 0.1250. Complex 1 possesses an infinite 1D polymeric chain structure consisting of the repeated basic four-membered ring units （Cd2O2） and eight-membered ring units （CdOCO）2. Compound 2displays a linear 1D chain through Mn（Ⅱ） atoms and bridging carboxylate groups of 3,5-dinitrosalicylic acid ligands with the Mn…Mn separation of 4.472（2）A. The fluorescence properties and cyclic voltammetric behaviors of the complexes are also reported.展开更多
Two complexes,NdL_3·2C_2H_5OH and NdL_3·2H_2O where L=cyclohexane-carboxylate anion,were synthesized and the structure of the former was determined by the single-crystal X-ray diffration method. The crystal ...Two complexes,NdL_3·2C_2H_5OH and NdL_3·2H_2O where L=cyclohexane-carboxylate anion,were synthesized and the structure of the former was determined by the single-crystal X-ray diffration method. The crystal is triclinic,Pspace group with the cell parameters:a=1.2385(6),b=1.2385(6),c=0.9421(5) nm.α=91.69(4)°,β=98.49(4)°,γ=99.16(5)°,Z=2,V=1.436 nm^3.The structure was refined to R value of 0.0866.Each Nd atom is connected with other two Nd atoms by two bidentate and two tridentate carboxyl groups to form a linear polymer.The Nd atom is further coordinated by a chelating carboxyl and two ethanol molecules.So the central atom is nine-coordinated with a distorted monocapped square-antiprism geometry.The infrared spectra and the thermal analysis of the complexes were also studied.展开更多
The title complex was obtained by reactions of [Mo(CO)_3(MeCN)_3] with [CuBr(pySH)(PPh_3)_2]or directly with pySH and PPh_3. The latter method can be used to synthesize the corresponding tungsten complex [W_2(CO)_4(μ...The title complex was obtained by reactions of [Mo(CO)_3(MeCN)_3] with [CuBr(pySH)(PPh_3)_2]or directly with pySH and PPh_3. The latter method can be used to synthesize the corresponding tungsten complex [W_2(CO)_4(μ-pyS)_2(PPh_3)_2].The molecular structure of the title compound was determined by X-ray diffraction method.展开更多
A series of 3-trichlorostannylpropionate complexes with dibutylsulfoxide and pyridine oxide were synthesized by transesterification reaction and characterized by means of elemental analysis, IR, NMR(H-1,C-13) and X-ra...A series of 3-trichlorostannylpropionate complexes with dibutylsulfoxide and pyridine oxide were synthesized by transesterification reaction and characterized by means of elemental analysis, IR, NMR(H-1,C-13) and X-ray single crystal diffraction.展开更多
A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemic...A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemical calculation.The calculated results are in good agreement with that obtained in the experiments.Three Cl atoms are on the same side of Ln in LnCl_3·15-C-5 and the crown ring on the other side.forming a complex molecule with coordination number 8.LnCl_3·15-C-5 is easily hygroscopic in air because of its unsaturated coordination,which differs sharply from the stable Ln(NO_3)_3·15-C-5 com- plex of coordination number 11.The HOMO and neighboring occupied MOs are composed of Cl 3p and O2p, and the LUMO and neighboring unoccupied MOs are composed of Ln orbitals.The level structure easily pro- duces Ln3d satellite in XPS caused by L→Ln charge transfer transition.Due to the coordination,the absolute values of the charge are decreased at Ln and O atoms,but increased at Cl atoms,which is in agreement with XPS results.展开更多
Eight new ZnⅡ-yⅢ and ZnⅡ-LnⅢ heterometallic Schiff base complexes： MZnL2（NO3）3 （M = Y （1）, La （2）, Pr （3）, Nd （4）, Eu （5）, Gd （6）, Dy （7）, Er （8）; L = 2-（（（2- （imidazo[1,5-a]pyridin-3-yl）p...Eight new ZnⅡ-yⅢ and ZnⅡ-LnⅢ heterometallic Schiff base complexes： MZnL2（NO3）3 （M = Y （1）, La （2）, Pr （3）, Nd （4）, Eu （5）, Gd （6）, Dy （7）, Er （8）; L = 2-（（（2- （imidazo[1,5-a]pyridin-3-yl）phenyl）imino）methyl）-6-methoxyphenol）, have been rationally synthesized under solvothermal conditions and characterized by IR, elemental analyses （EA）, single-crystal X-ray diffraction, and powder XRD. Furthermore, luminescence in the visible region for solids 1-8 suggested zine/ligand-centered emission at room temperature.展开更多
Reaction of WCl6, mpH2 o-mercaptophenol) and MeONa in the presence of Ph4PBr gave complexes (Ph4P)[W(mp)3] (1) and (Ph4P) CWO(OMe) (mp)2] (2). Crystal data complex (2), C37H31O4PS2W, Mr = 818. 61, monoclinic, space gr...Reaction of WCl6, mpH2 o-mercaptophenol) and MeONa in the presence of Ph4PBr gave complexes (Ph4P)[W(mp)3] (1) and (Ph4P) CWO(OMe) (mp)2] (2). Crystal data complex (2), C37H31O4PS2W, Mr = 818. 61, monoclinic, space group P2/a, a=26. 555(3), b=9. 634(1), c=13. 523(7) A. β=94. 68 (2)°, V=3448. 1 A3. A=1. 58 g/cm3, Z = 4. λ(MoKα)=0. 71073 A , μ= 36. 2 cm-1, F(000) = 1624, T=296K, final R(Rw) = 0. 068(0. 070) for 3929 observed reflections. The WO4S2 core is arranged in a distorted octahedral geometry.展开更多
The crystal structure of the title complex salt has been determined by single-crystal X-ray structure analysis. The crystal data are as follows; Monoclinic, P21/c, a=15.6480(10)A,b=16.7870(10)A, c=10.347(2)A, β=90.79...The crystal structure of the title complex salt has been determined by single-crystal X-ray structure analysis. The crystal data are as follows; Monoclinic, P21/c, a=15.6480(10)A,b=16.7870(10)A, c=10.347(2)A, β=90.790(10), V=2717.7(6)A3, Z=3, and R=0.0333 for 4789 unique reflections. The complex anion has a pseudo-octahedral structure distorted more than the CrⅢand CoⅢ analogs, in which cach iminodiacetato ligand (ida2-) is coordinated in a facial fashion with the two N atoms in a cis configuration, resulting in an unsyin-fac structure.展开更多
The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3（CO）_（12） with R-C≡C-R＇（R = Fc（Ferrocenyl）; R′ = Ph（Phenyl）, Fc, H）. The hexacarbonyldiiron cluster wit...The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3（CO）_（12） with R-C≡C-R＇（R = Fc（Ferrocenyl）; R′ = Ph（Phenyl）, Fc, H）. The hexacarbonyldiiron cluster with ferracyclopentadiene ring（μ_2, η~4-C_4Ph_4）Fe_2（CO）_6（1） and one tetraphenyl substituted cyclopentadienone（Ph_4C_4CO）（2） were simultaneously obtained by the reaction of Fe_3（CO）_（12） with alkyne（Ph-C≡C-Ph）. Only one ferrole cluster（μ_2, η~4-C_4Fc_2H_2）Fe_2（CO）_6（3） was separated by using Fc-C≡C-H as alkyne. One tri-carbonyl iron complex（η~4-C_4Fc_4CO）Fe（CO）_3（4） and an unexpected new cyclic ketone compound 2,2,4,5-tetraferrocenylcyclopenta-4-en-1,3-di-one [Fc_4C_3（CO）_2]（5） were obtained by using Fc-C≡C-Fc as alkyne. A new complex（η4-2,4-diphenyl-3,5-diferrocenylcyclopenta-2,4-dien-1-one）-tricarbonyl iron（η~4-C_4Ph_2Fc_2CO）Fe（CO）_3（6） was synthesized by the reaction of Fe_3（CO）_（12） with Fc-C≡C-Ph. The structures of compounds 1~6 were determined by X-ray single-crystal diffraction and spectroscopic characterization. The crystal structures of two new compounds 5 and 6 were analyzed. Our experimental results reveal the structural models of the reaction products are affected by the kinds of substituents from alkynes R-C≡C-R′.展开更多
Two complexes, [Cd（nphth）（2,2＇-bipy）（H20）]2.2H20 （1） and [Cd（nphth）（4,4＇- bipy）（H20）], （2） （nphth = 3-nitrophthalate, 2,2＇-bipy = 2,2＇-bipyridine, 4,4＇-bipy = 4,4＇-bipyridine）, were synthesized...Two complexes, [Cd（nphth）（2,2＇-bipy）（H20）]2.2H20 （1） and [Cd（nphth）（4,4＇- bipy）（H20）], （2） （nphth = 3-nitrophthalate, 2,2＇-bipy = 2,2＇-bipyridine, 4,4＇-bipy = 4,4＇-bipyridine）, were synthesized by hydrothermal reactions and structurally characterized. Complex 1 crystallizes in triclinic with space group Pi, a = 0.7599（4）, b = 1.0551（6）, c = 1.2448（6） nm, α = 88.96（2）, β = 75.40（2）, γ= 76.76（2）°, V= 0.9393（9） nm3, Z = 1, Dc = 1.816 Mg/m3, F（000） = 512, μ = 1.217 mm-1, S = 0.946, the final R = 0.0238 and wR = 0.0631, Complex 2 crystallizes in monoclinic, space group P21/c, a = 0.737（5）, b = 2.338（1）, c = 1.0030（6） nm, β = 96：359（9）°, V= 1.803（2） nm3, Z = 4, Dc = 1.826 Mg/m3, F （000） = 984,μ = 1.260 mm-1, S = 1.016, the final R = 0.0455 and wR = 0.1007. Complex 1 exhibits a discrete cyclic binuclear structure and complex 2 possesses a 2D layer structure with cyclic binuclear unit. The fluorescent spectrum study shows that complex 1 exhibits fluorescent emission in the solid state at room temperature.展开更多
Two new mononuclear complexes, namely [Co（L）2]（1） and [Mn（L）2]（2）（HL = N-（3-methylsalicylidene）tryptamine）, have been synthesized by the reactions of the ligand with cobalt acetate or manganese acetate in ...Two new mononuclear complexes, namely [Co（L）2]（1） and [Mn（L）2]（2）（HL = N-（3-methylsalicylidene）tryptamine）, have been synthesized by the reactions of the ligand with cobalt acetate or manganese acetate in anhydrous ethanol. The crystal structures of the complexes were characterized by IR spectrum, elemental analysis, PXRD and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in monoclinic, space group C2/c, with a = 23.146（2）, b = 9.4864（10）, c = 13.9261（15）A, β = 102.898（2）°, V = 2980.6（5） ？3, Z = 4, Dc = 1.367 g/cm3, F（000） = 1284 and μ = 0.616 mm^-1. Complex 2 crystallizes in monoclinic, space group P21/n, with a = 14.807（11）, b = 13.118（10）, c = 16.663（13） A, β = 111.237（14）°, V = 3017（4） A^3, Z = 4, Dc = 1.342 g/cm^3, F（000） = 1276 and μ = 0.477 mm-1. The units of complex 1 are linked by intermolecular N–H…π hydrogen bonds into infinite 1D chains, which are further extended into a 3D supramolecular structure by a series of π···π stacking interactions. The units of complex 2 are linked by intermolecular N–H…π hydrogen bonds and C–H…π hydrogen bonds into an infinite 3D supramolecular structure. Meanwhile, the antibacterial activities of the ligand and its complexes have been tested against four kinds of bacteria. The results show that the three compounds all have excellent antibacterial activities and that 1 and 2 possess stronger inhibiting effects against the bacteria than the Schiff base.展开更多
The Reliability-Based Design Optimization(RBDO)of complex engineering structures considering uncertainties has problems of being high-dimensional,highly nonlinear,and timeconsuming,which requires a significant amount ...The Reliability-Based Design Optimization(RBDO)of complex engineering structures considering uncertainties has problems of being high-dimensional,highly nonlinear,and timeconsuming,which requires a significant amount of sampling simulation computation.In this paper,a basis-adaptive Polynomial Chaos(PC)-Kriging surrogate model is proposed,in order to relieve the computational burden and enhance the predictive accuracy of a metamodel.The active learning basis-adaptive PC-Kriging model is combined with a quantile-based RBDO framework.Finally,five engineering cases have been implemented,including a benchmark RBDO problem,three high-dimensional explicit problems,and a high-dimensional implicit problem.Compared with Support Vector Regression(SVR),Kriging,and polynomial chaos expansion models,results show that the proposed basis-adaptive PC-Kriging model is more accurate and efficient for RBDO problems of complex engineering structures.展开更多
基金supported by the National Natural Science Foundation of China(No.21501037)the Natural Science Foundation of Hainan Province(No.20152017)the Science and Research Project of Education Department of Hainan Province(Nos.Hjkj2013-25 and Hnky2015-27)
文摘Two new fluorinated phenylisoquinoline-based iridium（Ⅲ） complexes,[Ir（f2piq）2（bipy）][PF6]（3a） and[Ir（fmpiq）2（bipy）][PF6]（3b）（f2piq = l-（2,4-difluorophenyl）isoquinoline,fmpiq = 1-（4-fluoro-2-methylphenyl）isoquinoline,bipy = 2,2＇-bipyridine）,have been synthesized and fully characterized.Single crystal X-ray diffraction study has been undertaken on complexes 3a and 3b,which show that each adopts the distorted octahedral coordination geometry with the cis-C,C＇ and trans-N,N＇ configuration.The photoluminescence spectra of 3a and 3b exhibit yellow and orange emission maxima at 584 and 600 nm,respectively.The frontier molecular orbital diagrams and the lowest-energy electronic transitions of 3a-3b have been calculated with density functional theory（DFT） and time-dependent DFT（TD-DFT）.The absorption and emission spectra of complex 3b is red-shifted relative to those of complex 3a,as a consequence of the nature of the methyl group.
基金Supported by the National Natural Science Foundation of China(No.21061003)
文摘The two complexes [HgI_2L]（DMF）（1） and [AgL_2]（ClO_4）（CH_3CN）（2） were synthesized from the reaction of Schiff base ligand（2-acetylpyridine-p-aminobenzoylhydrazone）（L） with HgI_2 or AgClO_4 respectively. The compounds are characterized by ^1H NMR,FTIR and elemental analysis. The structures of the ligand and two complexes are measured via single-crystal X-ray diffraction. In these two complexes,the structures are both distorted triangular bipyramids with five-coordinated centers.
基金Project supported by the China National"863"Program
文摘A new stripping agent N,N-dimethyl-3-oxa-glutaramic Acid (DOGA) was used in TRPO process to simplify the TRPO process. The structures of the complexes of the DOGA with Eu(Ⅲ), Nd(Ⅲ), La(Ⅲ) were characterized with extended X-ray absorption fine structure spectroscopy (EXAFS), infrared spectra (IR) and mass spectra (MS). The molecular formula of the complexes of Eu(Ⅲ) and Nd(Ⅲ) is deduced to be M(DOGA)_3, and only La(Ⅲ) can form the complex HM(DOGA)_4 under condition of high consistency of the DOGA. The coordination number of Ln(Ⅲ) in the complexes is 8, and all of coordinated donor atoms are O atoms. For Eu(Ⅲ), Nd(Ⅲ), the coordination numbers of O atom in the first coordination shell is 6 and the average coordination bond lengths of Ln-O are 0 240 nm, 0 244 nm respectively, while the numbers of the second O shell are 2.4, and the average coordination bond lengths of Ln-O are 0 260 nm, 0 262 nm. For La(Ⅲ), the coordination numbers of O atom in the first coordination shell is 6 and the average coordination bond lengths of La-O are 0 258 nm, while the number of O atom in the second coordination shell is 4.4, and the average coordination bond length of La-O is 0 28 nm. The results of IR and MS show that there is no water coordinating with Ln(Ⅲ) in the complexes.
文摘A new kind of Schiff base HL（HL= 1-phenyl-3-methyl-4-（p-methylbenzoyl）-5-pyrazolone with L-Leucine methyl ester） and complexes Ni L′_2·0.75C_2H_5OH·0.25H_2O,Cu L′′2（L′ = 1-phenyl-3-methyl-4-（p-methylbenzoyl）-5-pyrazolone with L-leucine ethyl,L′′ = 1-phenyl-3-methyl-4-（p-methylbenzoyl）-5-pyrazolone with L-leucine） have been synthesized and structurally determined by X-ray diffraction. For HL： crystal structure determination indicates that there are two independent HLs with different conformations in one asymmetric unit. For complex 1： the Ni（Ⅱ） ion is six-coordinated by two carbonyl oxygen atoms from pyrazolone ring,two nitrogen atoms from different HL′ and two oxygen atoms from L-Leucine ethyl ester to form a distorted octahedral geometry. For complex 2： the Cu（Ⅱ） ion is four-coordinated by one carbonyl oxygen atom from the pyrazolone ring,one nitrogen atom from HL′′,and two different carboxylic oxygen atoms from L-leucine with the same conformation to form a distorted quadrilateral geometry.
基金financially supported by the National Natural Science Foundation of China (No.21172190)the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘The functionalized calix[4]pyrrole meso-substituted Schiff bases were conveniently prepared by four- step synthetic route. Furthermore, the nickel and copper complexes of calix[4]pyrrole meso-substituted Schiff base with 1：2 stoichiometry were obtained. The crystal structures of the calix[4]pyrroles and their metal complexes were determined by X-ray diffraction.
基金supported by the Science and Technology Development Project of Jilin Provincial Science&Technology Department(201205080)the Science and Technology Research Projects of the Education Office of Jilin Province(No.2013.384)
文摘Two new complexes [Ag（bix）]n·n NAA·n H2O（1） and [Cd（NAA）（phen）2（H2O）]2· 2CH3COO-·H2O（2）（bix = 1,4-bis（imidazol-1-ylmethyl）benzene,HNAA = α-naphthylacetic acid,phen = 1,10-phenanthroline） have been successfully synthesized under hydrothermal conditions.Their structures have been determined by elemental analyses,IR spectroscopy,TG and single-crystal X-ray diffraction analysis.The intermolecular hydrogen bonding or π-π stacking interactions extend the complexes into a 3D supramolecular structure.Moreover,the luminescent properties of complex 2 have been investigated in the solid state.
基金The project was supported by Youth Science Foundation of Shandong University
文摘Reaction of ferrocenoyl chloride with [Et;NH] [（μ-CO）(μ-RS) Fe;=（CO）;] complexes gave bridging ferrocenoyl complexes（μ-FcCO）(μ-RS)Fe;（CO）;（Fc=ferrocenyl, R=Et, i-Pr, n-Bu, t-Bu, Ph）.The structures of all new complexes were characterised by;HNMR, IR and MS.
基金the National Natural Science Foundation of China (No. 20431010)
文摘The two title complexes, [Cd{3,5-（NO2）2sal}（2,2′-bipy）]n 1 and [Mn{3,5- （NO2）2sal}（2,2′-bipy）]n 2 （3,5-（NO2）2sal = 3,5-dinitrosalicylate, 2,2＇-bipy = 2,2′-bipyridine）, were synthesized by the hydrothermal reaction and structurally characterized. Complex 1 crystallizes in triclinic, space group P1, a = 5.581（4）, b = 12.071（8）, c = 12.88（1）A, α= 92.10（3）,β= 96.73（3）, γ = 102.02（2）°, C17H10N407Cd, Mr = 494.69, V= 841（1）A3, Z = 2, Dc = 1.954 g/cm3, F（000） = 488, μ= 1.353 mm^-1, R = 0.0248 and wR = 0.0761. Complex 2 crystallizes in monoclinic with space group P21/c, a = 8.604（3）, b = 23.88（1）, c = 8.894（3） A, β = 102.45（1）°, C17H10N407Mn, Mr = 437.23, V= 1785（1） A3, Z=.4, Dc = 1.627 g/cm3, F（000） = 884, μ = 0.791 mm^-1, R = 0.0471 and wR = 0.1250. Complex 1 possesses an infinite 1D polymeric chain structure consisting of the repeated basic four-membered ring units （Cd2O2） and eight-membered ring units （CdOCO）2. Compound 2displays a linear 1D chain through Mn（Ⅱ） atoms and bridging carboxylate groups of 3,5-dinitrosalicylic acid ligands with the Mn…Mn separation of 4.472（2）A. The fluorescence properties and cyclic voltammetric behaviors of the complexes are also reported.
文摘Two complexes,NdL_3·2C_2H_5OH and NdL_3·2H_2O where L=cyclohexane-carboxylate anion,were synthesized and the structure of the former was determined by the single-crystal X-ray diffration method. The crystal is triclinic,Pspace group with the cell parameters:a=1.2385(6),b=1.2385(6),c=0.9421(5) nm.α=91.69(4)°,β=98.49(4)°,γ=99.16(5)°,Z=2,V=1.436 nm^3.The structure was refined to R value of 0.0866.Each Nd atom is connected with other two Nd atoms by two bidentate and two tridentate carboxyl groups to form a linear polymer.The Nd atom is further coordinated by a chelating carboxyl and two ethanol molecules.So the central atom is nine-coordinated with a distorted monocapped square-antiprism geometry.The infrared spectra and the thermal analysis of the complexes were also studied.
文摘The title complex was obtained by reactions of [Mo(CO)_3(MeCN)_3] with [CuBr(pySH)(PPh_3)_2]or directly with pySH and PPh_3. The latter method can be used to synthesize the corresponding tungsten complex [W_2(CO)_4(μ-pyS)_2(PPh_3)_2].The molecular structure of the title compound was determined by X-ray diffraction method.
文摘A series of 3-trichlorostannylpropionate complexes with dibutylsulfoxide and pyridine oxide were synthesized by transesterification reaction and characterized by means of elemental analysis, IR, NMR(H-1,C-13) and X-ray single crystal diffraction.
文摘A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemical calculation.The calculated results are in good agreement with that obtained in the experiments.Three Cl atoms are on the same side of Ln in LnCl_3·15-C-5 and the crown ring on the other side.forming a complex molecule with coordination number 8.LnCl_3·15-C-5 is easily hygroscopic in air because of its unsaturated coordination,which differs sharply from the stable Ln(NO_3)_3·15-C-5 com- plex of coordination number 11.The HOMO and neighboring occupied MOs are composed of Cl 3p and O2p, and the LUMO and neighboring unoccupied MOs are composed of Ln orbitals.The level structure easily pro- duces Ln3d satellite in XPS caused by L→Ln charge transfer transition.Due to the coordination,the absolute values of the charge are decreased at Ln and O atoms,but increased at Cl atoms,which is in agreement with XPS results.
基金supported by the National Natural Science Foundation of China(21272167 and 21201127)Starting-up Foundation(Q410900111 and Q410900211)+1 种基金Scientific Research Foundation of Soochow University(SDY2012A07)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
文摘Eight new ZnⅡ-yⅢ and ZnⅡ-LnⅢ heterometallic Schiff base complexes： MZnL2（NO3）3 （M = Y （1）, La （2）, Pr （3）, Nd （4）, Eu （5）, Gd （6）, Dy （7）, Er （8）; L = 2-（（（2- （imidazo[1,5-a]pyridin-3-yl）phenyl）imino）methyl）-6-methoxyphenol）, have been rationally synthesized under solvothermal conditions and characterized by IR, elemental analyses （EA）, single-crystal X-ray diffraction, and powder XRD. Furthermore, luminescence in the visible region for solids 1-8 suggested zine/ligand-centered emission at room temperature.
文摘Reaction of WCl6, mpH2 o-mercaptophenol) and MeONa in the presence of Ph4PBr gave complexes (Ph4P)[W(mp)3] (1) and (Ph4P) CWO(OMe) (mp)2] (2). Crystal data complex (2), C37H31O4PS2W, Mr = 818. 61, monoclinic, space group P2/a, a=26. 555(3), b=9. 634(1), c=13. 523(7) A. β=94. 68 (2)°, V=3448. 1 A3. A=1. 58 g/cm3, Z = 4. λ(MoKα)=0. 71073 A , μ= 36. 2 cm-1, F(000) = 1624, T=296K, final R(Rw) = 0. 068(0. 070) for 3929 observed reflections. The WO4S2 core is arranged in a distorted octahedral geometry.
文摘The crystal structure of the title complex salt has been determined by single-crystal X-ray structure analysis. The crystal data are as follows; Monoclinic, P21/c, a=15.6480(10)A,b=16.7870(10)A, c=10.347(2)A, β=90.790(10), V=2717.7(6)A3, Z=3, and R=0.0333 for 4789 unique reflections. The complex anion has a pseudo-octahedral structure distorted more than the CrⅢand CoⅢ analogs, in which cach iminodiacetato ligand (ida2-) is coordinated in a facial fashion with the two N atoms in a cis configuration, resulting in an unsyin-fac structure.
基金supported by the National Natural Science Foundation of China(Nos.21266019,21062011 and 21462029)Inner Mongolia Autonomous Region Higher Scientific Research Project(NJZY14060)
文摘The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3（CO）_（12） with R-C≡C-R＇（R = Fc（Ferrocenyl）; R′ = Ph（Phenyl）, Fc, H）. The hexacarbonyldiiron cluster with ferracyclopentadiene ring（μ_2, η~4-C_4Ph_4）Fe_2（CO）_6（1） and one tetraphenyl substituted cyclopentadienone（Ph_4C_4CO）（2） were simultaneously obtained by the reaction of Fe_3（CO）_（12） with alkyne（Ph-C≡C-Ph）. Only one ferrole cluster（μ_2, η~4-C_4Fc_2H_2）Fe_2（CO）_6（3） was separated by using Fc-C≡C-H as alkyne. One tri-carbonyl iron complex（η~4-C_4Fc_4CO）Fe（CO）_3（4） and an unexpected new cyclic ketone compound 2,2,4,5-tetraferrocenylcyclopenta-4-en-1,3-di-one [Fc_4C_3（CO）_2]（5） were obtained by using Fc-C≡C-Fc as alkyne. A new complex（η4-2,4-diphenyl-3,5-diferrocenylcyclopenta-2,4-dien-1-one）-tricarbonyl iron（η~4-C_4Ph_2Fc_2CO）Fe（CO）_3（6） was synthesized by the reaction of Fe_3（CO）_（12） with Fc-C≡C-Ph. The structures of compounds 1~6 were determined by X-ray single-crystal diffraction and spectroscopic characterization. The crystal structures of two new compounds 5 and 6 were analyzed. Our experimental results reveal the structural models of the reaction products are affected by the kinds of substituents from alkynes R-C≡C-R′.
基金supported by the National Natural Science Foundation of China(21371088)the Education Department of Fujian Province(No.JK2012048,JA12310,JB12207)
文摘Two complexes, [Cd（nphth）（2,2＇-bipy）（H20）]2.2H20 （1） and [Cd（nphth）（4,4＇- bipy）（H20）], （2） （nphth = 3-nitrophthalate, 2,2＇-bipy = 2,2＇-bipyridine, 4,4＇-bipy = 4,4＇-bipyridine）, were synthesized by hydrothermal reactions and structurally characterized. Complex 1 crystallizes in triclinic with space group Pi, a = 0.7599（4）, b = 1.0551（6）, c = 1.2448（6） nm, α = 88.96（2）, β = 75.40（2）, γ= 76.76（2）°, V= 0.9393（9） nm3, Z = 1, Dc = 1.816 Mg/m3, F（000） = 512, μ = 1.217 mm-1, S = 0.946, the final R = 0.0238 and wR = 0.0631, Complex 2 crystallizes in monoclinic, space group P21/c, a = 0.737（5）, b = 2.338（1）, c = 1.0030（6） nm, β = 96：359（9）°, V= 1.803（2） nm3, Z = 4, Dc = 1.826 Mg/m3, F （000） = 984,μ = 1.260 mm-1, S = 1.016, the final R = 0.0455 and wR = 0.1007. Complex 1 exhibits a discrete cyclic binuclear structure and complex 2 possesses a 2D layer structure with cyclic binuclear unit. The fluorescent spectrum study shows that complex 1 exhibits fluorescent emission in the solid state at room temperature.
基金supported by the National Natural Science Foundation of China(No.21272008)the Natural Science Industry-University-Research Foundation of Suzhou University(2015hx014)
文摘Two new mononuclear complexes, namely [Co（L）2]（1） and [Mn（L）2]（2）（HL = N-（3-methylsalicylidene）tryptamine）, have been synthesized by the reactions of the ligand with cobalt acetate or manganese acetate in anhydrous ethanol. The crystal structures of the complexes were characterized by IR spectrum, elemental analysis, PXRD and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in monoclinic, space group C2/c, with a = 23.146（2）, b = 9.4864（10）, c = 13.9261（15）A, β = 102.898（2）°, V = 2980.6（5） ？3, Z = 4, Dc = 1.367 g/cm3, F（000） = 1284 and μ = 0.616 mm^-1. Complex 2 crystallizes in monoclinic, space group P21/n, with a = 14.807（11）, b = 13.118（10）, c = 16.663（13） A, β = 111.237（14）°, V = 3017（4） A^3, Z = 4, Dc = 1.342 g/cm^3, F（000） = 1276 and μ = 0.477 mm-1. The units of complex 1 are linked by intermolecular N–H…π hydrogen bonds into infinite 1D chains, which are further extended into a 3D supramolecular structure by a series of π···π stacking interactions. The units of complex 2 are linked by intermolecular N–H…π hydrogen bonds and C–H…π hydrogen bonds into an infinite 3D supramolecular structure. Meanwhile, the antibacterial activities of the ligand and its complexes have been tested against four kinds of bacteria. The results show that the three compounds all have excellent antibacterial activities and that 1 and 2 possess stronger inhibiting effects against the bacteria than the Schiff base.
基金supported by the National Key R&D Program of China(No.2021YFB1715000)the National Natural Science Foundation of China(No.52375073)。
文摘The Reliability-Based Design Optimization(RBDO)of complex engineering structures considering uncertainties has problems of being high-dimensional,highly nonlinear,and timeconsuming,which requires a significant amount of sampling simulation computation.In this paper,a basis-adaptive Polynomial Chaos(PC)-Kriging surrogate model is proposed,in order to relieve the computational burden and enhance the predictive accuracy of a metamodel.The active learning basis-adaptive PC-Kriging model is combined with a quantile-based RBDO framework.Finally,five engineering cases have been implemented,including a benchmark RBDO problem,three high-dimensional explicit problems,and a high-dimensional implicit problem.Compared with Support Vector Regression(SVR),Kriging,and polynomial chaos expansion models,results show that the proposed basis-adaptive PC-Kriging model is more accurate and efficient for RBDO problems of complex engineering structures.
