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1.
Homogeneous fields of Sr4 − x M x Nb2O9 (M = Cd, Cu, Ni, or Zn) solid solutions were determined using powder X-ray diffraction. Phase fields were plotted proceeding from the tolerance factor t and electronegativity ratio $ \bar k_A /\bar k_B $ \bar k_A /\bar k_B with a satisfactory fit of experimental results. Thermogravimetry was used to establish the major kinetic laws of solid-phase synthesis (conversion, rate-controlling stage, and effective activation energy) in (4 − x)SrCO3 + xMO + Nb2O5 powdery mixtures. Direct radiometry was used to determine 90Sr, 63Ni, and 65Zn self-diffusion coefficients in solid solutions based on the Sr4Nb2O9 phase. Electrical conductivity was measured as a function of temperature for all Sr4Nb2O9-“M4Nb2O9” samples. The conductivity of Sr4 − x M x Nb2O9 (M = Cd, Cu, Ni, or Zn) solid solutions has a mixed ion-electron character.  相似文献   

2.
New mixed-ligands complexes with empirical formulae: M(2,4′-bpy)2L2·H2O (M(II)Zn, Cd), Zn(2-bpy)3L2·4H2O, Cd(2-bpy)2L2·3H2O, M(phen)L2·2H2O (where M(II)=Mn, Ni, Zn, Cd; 2,4′-bpy=2,4′-bipyridine, 2-bpy=2,2′-bipyridine, phen=1,10-phenanthroline, L=HCOO) were prepared in pure solid state. They were characterized by chemical, thermal and X-ray powder diffraction analysis, IR spectroscopy, molar conductance in MeOH, DMF and DMSO. Examinations of OCO absorption bands suggest versatile coordination behaviour of obtained complexes. The 2,4′-bpy acts as monodentate ligand; 2-bpy and phen as chelating ligands. Thermal studies were performed in static air atmosphere. When the temperature raised the dehydration processes started. The final decomposition products, namely MO (Ni, Zn, Cd) and Mn3O4, were identified by X-ray diffraction.  相似文献   

3.
The first salt‐like compounds of dications with [AuCl4] anions are reported. The compounds Zn[AuCl4]2 · (AuCl3)1.115 ( 1 ) and Cd[AuCl4]2 ( 2 ) are obtained from reactions of MCl2 (M = Zn, Cd) and elemental gold in liquid chlorine at ambient temperature under autogenous pressure and subsequent annealing at 230 °C. The structure of 1 represents an incommensurately modulated composite [superspace group C2/c(α0γ)0s] built of two subsystems. The first subsystem contains chains of zinc(II) tetrachloridoaurate(III), which feature a slightly distorted octahedral coordination of Zn and can be described by the Niggli formula 1{Zn[AuCl4]1/1[AuCl4]2/2}. The second subsystem consists of Au2Cl6 molecules, which are located in channels built up by the first subsystem. The structural parameters of the hosted Au2Cl6 molecules show only small deviations from neat AuCl3. The crystal structure of Cd[AuCl4]2 ( 2 ) consists of chains built of Cd2+ ions coordinated by bridging [AuCl4] anions and alternating Cd‐Au sequence. Cd has a distorted octahedral coordination environment.  相似文献   

4.
Three linear trinuclear Schiff base complexes, {Zn[Zn(CH3COO)(C17H16N2O2)]2} ( 1 ), {Zn[Zn(CH3COO)(C25H20N2O2)]2} ( 2 ), and {Cd[Cd(CH3COO)(C18H18N2O2)]2} ( 3 ), were synthesized for the first time under solvolthermal conditions. Their structures have been characterized by elemental analyses, X-ray single crystal determinations, and infrared spectroscopy. There are three bridges across the M-M atom pairs (M is Zn for 1 and 2 , or Cd for 3 ) in each complex, involving two O atoms of a Schiff base ligand (N,N′-bis(salicylidene)-1, 3-propanediaminate (SALPD2-) for 1 , N, N′-bis(2-hydroxy-naphthalmethenylimino)-1, 3-propanediaminate (NAPTPD2-) for 2 , and N,N′-bis-(salicylidene)-1,4-butanediaminate (SALBD2-) for 3 ), and an O-C-O moiety of a μ-acetato group. In each of the complexes, the central M2+ ion is located on an inversion center and has a distorted octahedral coordination involving four bridging O atoms from two Schiff base ligands in the equatorial plane and one O atom from each bridging acetate group in the axial positions. The coordination around the terminal M2+ ions is irregular square pyramidal, with two O atoms and two N atoms of the Schiff base ligand in the basal plane and one O atom from an acetate group in the apical position. The acetate bridges linking the central and terminal M2+ ions are mutually trans. The M…M distances are 3.050(3) Å in 1 , 3.139(2) Å in 2 , and 3.287(6) Å in 3 .  相似文献   

5.
From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M 2+ (aq) + 1 · Sr2+ (nb) ⇄ 1 · M 2+ (nb) + Sr2+ (aq) taking place in the two-phase water-nitrobenzene system (M 2+ = Cu2+, Zn2+, Cd2+, Pb2+, UO2 2+, Fe2+, Co2+, and Ni2+; 1 = valinomycin; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Moreover, the stability constants of the 1 · M 2+ complexes in water saturated nitrobenzene were calculated; they were found to increase in the order Fe2+ < Cd2+, Co2+ < Ni2+ < UO2 2+, Zn2+ < Cu2+ < Pb2+.  相似文献   

6.
The reactions of LnI2 (Ln = Nd (1) or Dy (2)) with cyclopentadiene (CpH) in THF at 0 °C afforded the CpLnI2(THF)3 complexes in 65—67% yields. The reaction of thulium diiodide (3) with an excess of CpH at 60 °C produced CpTmI2(THF)3, Cp2TmI(THF)2, and TmI3(THF)3 in 21, 58, and 63% yields, respectively. The reactions of 1 and 2 with pentamethylcyclopentadiene (Cp*H) in THF were accompanied by disproportionation giving rise to the Cp*2LnI(THF)2 and LnI3(THF) x complexes. Neodymium triiodide was isolated in the ionic form [NdI2(THF)5]+[NdI4(THF)2]. Its structure and the structure of CpTmI2(THF)3 were established by X-ray diffraction analysis.  相似文献   

7.
Two unsymmetrical, macrocyclic, heterodinuclear complexes, [CuIIMII(L)]?(ClO4)2·nH2O (n?=?3; M?=?Zn, Cd) have been obtained by cyclocondensation of N,N′-bis(3-formyl-5-n-butylsalicylidene)ethylenediimine and 1,3-diaminopropane in the presence of M2+. The structures of both complexes were determined by X-ray diffraction techniques. In each complex, two metals are located in the tetraimine macrocyclic cavity, and a water molecule and a perchlorate group are separately coordinated to the metal ions on the same side of the ring. Coordination geometry around each metal is approximately square pyramidal. ESMS spectra were used to characterize the complexes and isotopic distributions were investigated.  相似文献   

8.
A number of uranoarsenates of alkali metals (Li+, Na+, K+, Rb+, Cs+, NH4+), alkaline-earth metals (Mg2+, Ca2+, Sr2+, Ba2+), and rare-earth metals (Y3+, La3+, Ln3+) of the composition M k (AsUO6) k · nH2O were prepared by ion exchange in the M k -HAsUO6 · 4H2O system. On the basis of the data of X-ray diffraction, IR spectroscopy, thermal analysis, and elemental analysis, molecular water and the nature of the interlayer atom M k were found to play the key role in structure formation for the compounds.  相似文献   

9.
From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M 2+ (aq) + 1 · Sr2+ (nb) ⇄ 1 · M 2+ (nb) + Sr2+ (aq) taking place in the two-phase water-nitrobenzene system (M 2+ = Cu2+, Zn2+, Cd2+, Pb2+, UO2 2+, Fe2+, Co2+, and Ni2+; 1 = valinomycin; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Moreover, the stability constants of the 1 · M 2+ complexes in water saturated nitrobenzene were calculated; they were found to increase in the order Fe2+ < Cd2+, Co2+ < Ni2+ < UO2 2+, Zn2+ < Cu2+ < Pb2+. Correspondence: Emanuel Makrlík, Faculty of Applied Sciences, University of West Bohemia, Pilsen, Czech Republic.  相似文献   

10.
The preparation of uncharged complexes with metal amide bonds of type [MeN4]±0 (Me = Zn2+, Cr2+ is reported. These compounds are obtained by the interaction between Zn(C6H5)2 or Cr(C6H5)3 · 3 THF and 2-[β-(phenyl-amino)-ethyl]-pyridine (I). The same complexes are formed by the reaction between ZnCl2 · 2 THF, CrBr2 · 2 THF, or CrCl3 · 3 THF and the lithium amide (II), which is prepared from (I) and phenyl lithium. The structure of the chromium(II) complex is discussed on the basis of magnetic and visible absorption measurements.  相似文献   

11.
Self‐assembly of Zn (II) or Cd (II) nitrates, flexible bis (pyridyl)‐diamine, as well as arenesulfonic acids, leads to the formation of ten coordination polymers, namely, [Zn(L1)(H2O)3]·2(p‐TS)·2H2O ( 1 ), [Zn(L1)(H2O)2]·2(p‐TS)·2H2O ( 2 ), [Zn(L1)2(p‐TS)2] ( 3 ), [Zn(H2L1)(H2O)4]·2(1,5‐NDS)·2H2O ( 4 ), [Zn(H2L2)(H2O)4]·2(1,5‐NDS)·4MeOH ( 5 ), [Cd(L1)(p‐TS)(NO3)]·H2O ( 6 ), [Cd(L1)(1,5 ‐NDS)0.5(H2O)]·0.5(1,5‐NDS)·H2O ( 7 ), [Cd(L2)(H2O)2]·(p‐TS)·(NO3)·3H2O ( 8 ), [Cd(L2)(1,5‐NDS)] ( 9 ) and [Cd(L2)(1,5‐NDS)]·MeOH ( 10 ) (L1 = N,N′‐bis (pyridin‐4‐ylmethyl) ethane‐1,2‐diamine, L2 = N,N′‐bis (pyridin‐3‐ylmethy l)ethane‐1,2‐diamine, p‐HTS = p‐toluenesulfonic acid, 1,5‐H2NDS = 1,5‐naphthalene disulfonic acid), which have been characterized by elemental analysis, IR, TG, PL, powder and single‐crystal X‐ray diffraction. Complexes 1 , 4 , 5 and 6 present linear or zigzag chain structures accomplished by the interconnection of adjacent M (II) cations through L1 ligands or protonated H2L12+/H2L22+ cations, while complexes 2 , 3 and 8 show similar (4,4) layer motifs constructed from the connection of M (II) cations through L1 and L2. The same coordination modes of L1 and L2 in complexes 7 and 9 join adjacent Cd (II) cations to form double chain structures, which are further connected by bis‐monodentate 1,5‐NDS2? dianions into different (6,3) and (4,4) layer motifs. The L2 molecules in complex 10 join adjacent Cd (II) cations together with 1,5‐NDS2? dianions to form 3D network with hxl topology. Therefore, the diverse coordination modes of the bis (pyridyl) ligand with chelating spacer and the feature of different arenesulfonate anions can effectively influence the architectures of these complexes. Luminescent investigation reveals that the emission maximum of these complexes varies from 374 to 448 nm in the solid state at room temperature, in which complexes 4 , 5 , 7 , 9 and 10 show average luminescence lifetimes from 7.20 to 14.82 ns. Moreover, photocatalytic properties of complexes 7–10 towards Methylene blue under Xe lamp irradiation are also discussed.  相似文献   

12.
12CaO?·?7Al2O3 doped with lanthanide is characterized by remarkable and technologically important up-conversion emission. However, the low up-conversion efficiency still remains the main limitation for practical applications. To improve the efficiency, bivalent alkaline earth ions (Mg2+, Sr2+, Ba2+)-tridoped Tm3+/Yb3+/12CaO?·?7Al2O3 were synthesized through a high-temperature solid-state reaction. The up-conversion luminescence properties of the samples were investigated by X-ray diffraction, fluorescence spectral measurement pump power, and fluorescence decay curves. The luminescence intensity of samples was significantly enhanced by bivalent alkaline earth ions. 12CaO?·?7Al2O3 doped with Sr2+ ions has stronger effects on up-conversion enhancement, which is better than Mg2+ and Ba2+. The up-conversion emission intensity was enhanced by 318 times and the red emission intensity by 218 times with 10?mol% Sr2+ ion. Additionally, the blue and red up-conversion emission peaks at 475 and 650?nm corresponding to energy transitions of 1G43H6 and 1G43F4, 3F23H6 were characterized using steady-state rate equations.  相似文献   

13.
Five novel coordination polymers, [(Cu(L1)2OH) · Cl · 3H2O] ( 1 ) [L1 = bis(N‐imidazolyl)methane], [Cd(L1)2(NCS)2] ( 2 ), [Zn(L1)2(NCS)2] ( 3 ), [Cu(L1)2(NO3)2] ( 4 ), and [Cu(L2)1.5(NCS)2] ( 5 ) [L2 = 1,4‐bis(N‐imidazolyl)butane] were obtained from self‐assembly of the corresponding metal salts with flexible ligands and their structures were fully characterized by X‐ray diffraction (XRD) analysis, Fourier Transform Infrared (FT‐IR) spectroscopy, elemental analysis and thermogravimetric (TGA) measurements. X‐ray diffraction analyses revealed that complexes 1 , 2 , 3 , and 4 exhibit 1D double‐stranded chain structures, which result from doubly bridged [CuOH], [M(NCS)2] (M = Cd, Zn), and [Cu(NO3)2] units, respectively. The polymeric copper complex 5 displays 1D ladder structure., These complexes, with the exception of complex 1 , are stable up to 300 °C.  相似文献   

14.
The binary and ternary systems M'O(M'CO3)-Nb2O5 and M'O(M'CO3)-MO-Nb2O5, where M'=Ca,Sr and Ba and M=Cu, Ni, Cd, Zn and Pb, were investigated by means of thermal analysis in the temperature range 20–1500°C. The boundaries of stability of the solid solutions Sr2−xMexNb2O7,Sr2−xMxNb2O7, Sr4−xMxNb2O9 and Sr6−xMxNb2O11 were determined by means of X-ray diffraction, and IR and Raman spectroscopy. The possibility of prognostication of the phase fields of stable solid solutions by calculation from the diagrams of the ‘comparative electronegativity of atoms vs. tolerance factor’ was demonstrated. The kinetic parameters of the interactions in theSrCO3+MO+Nb2O5 powder mixtures were established. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   

15.
Maghemite nano-particles were synthesized by a solid-state chemical reaction for its highly selective use as, cyclotron-produced, 109Cd (462.9 days) purification method of choice. 109Cd radiochemical separation starts with Ag activities precipitated with HCl 0.0015 M followed by, on a second step, 109Cd separation from Cu carrier and 65Zn (243.8 days) using Ca (NO3)2 0.01 M. Experimental parameters such, pH and sorbent concentration, on 109Cd extraction efficiency were investigated. Phase morphology, nanostructure and size of nano-particles were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). A 10–20 nm average grain size was derived from XRD line broadening and SEM data. Heat treatment on Fe3+:Fe2+ ratios equal to 2:1, produced powders, resulting in tetragonal (maghemite) structure at 300 °C and rhombohedra (hematite) at 600 °C. 109Cd chemical and radionuclidic purity were determined by ICP-AES and HPGe detector gamma-ray spectrometry. The overall recovery and radionuclide purity were 80.0% from obtained 129.63 kBq/C MeV (70 kBq/μAh) initial activity and 91.4%, respectively.  相似文献   

16.
Reduction of 2,5-di-tert-butylcyclopentadienone with two equivalents of thulium diiodide in tetrahydrofuran afforded the binuclear thulium(iii) complex with the cyclopentadienyl oxide ligand, viz., TmI2(THF)2[5-But 2C5H2O]TmI2(THF)3 (1). Shielding of the carbonyl carbon atom with two tert-butyl substituents prevents pinacolization of the ketyl radical anions that formed upon one-electron reduction of cyclopentadienone. The reaction of thulium diiodide with an excess of pyridine in tetrahydrofuran gave a product of reductive coupling of two pyridine radical anions, viz., [TmI2(C5H5N)4]2(2-N2C10H10) (2). The structures of complexes 1 and 2 were established by single-crystal X-ray diffraction analysis.  相似文献   

17.
Sr2CeO4/Ln3+ (Ln = Er, Ho, Tm) phosphors were synthesized with the microwave radiation method for the first time. The luminescent properties of the samples were investigated and the up-conversion luminescence of Er3+, Ho3+ and Tm3+ doped Sr2CeO4 phosphors was observed. The spectra indicate that the energy transfer takes place from the triplet excited state of MLCT (metal-to-ligand charge transfer) state for Sr2CeO4 (sensitizer) to the rare earth ions (activator). __________ Translated from Journal of Hebei Normal University (Natural Science Edition), 2007, 31(2): 212–216 [译自: 河北师范大学学报 (自然科学版)]  相似文献   

18.
The compounds [Cu(pmda)(crea)]·H2O ( 1 ), [Zn(pmda)(crea)]·H2O ( 2 ) and [Co(pmda)(crea)(H2O)]·H2O ( 3 ) were prepared and characterized by thermal, spectral and X‐ray diffraction methods. In compounds 1 and 2 the MII coordination is of type 4+1 and approaches to a trigonal bipyramid (71.85 and 86.18 %, respectively) with rather linear N(pmda)‐MII‐N(crea) trans‐apical angles, but with different longest coordination bond (Cu‐O(pmda) or Zn‐N(apliphatic, pmda), respectively). Both compounds are isotypic and one intra‐molecular interligand N‐H···O interaction reinforces the molecular recogniton crea‐MII(pmda) chelate. In contrast, the compound 3 exhibits an octahedral coordination, imposed by the 3d7 electronic configuration of the cobalt(II) atom, and the crea‐chelate recognition involves the Co‐N(crea) coordination bond and one intramolecular ‘bifurcated’ H‐bonding interaction between one N‐H(crea) bond and one O(pmda) plus the O(aqua) atoms as ‘acceptors’.  相似文献   

19.
The transition metal complexes with the ligand 1,3‐bis(N,N,N′,N′‐tetramethylguanidino)propane (btmgp), [Mn(btmgp)Br2] ( 1 ), [Co(btmgp)Cl2] ( 2 ), [Ni(btmgp)I2] ( 3 ), [Zn(btmgp)Cl2] ( 4 ), [Zn(btmgp)(O2CCH3)2] ( 5 ), [Cd(btmgp)Cl2] ( 6 ), [Hg(btmgp)Cl2] ( 7 ) and [Ag2(btmgp)2][ClO4]2·2MeCN ( 8 ), were prepared and characterised for the first time. The stoichiometric reaction of the corresponding water‐free metal salts with the ligand btmgp in dry MeCN or THF resulted in the straightforward formation of the mononuclear complexes 1 – 7 and the binuclear complex 8 . In complexes with MII the metal ion shows a distorted tetrahedral coordination whereas in 8 , the coordination of the MI ion is almost linear. The coordination behavior of btmgp and resulting structural parameters of the corresponding complexes were discussed in an comparative approach together with already described complexes of btmgp and the bisguanidine ligand N1,N2‐bis(1,3‐dimethylimidazolidin‐2‐ylidene)‐ethane‐1,2‐diamine (DMEG2e), respectively.  相似文献   

20.
The crystal structures among M1–M2–(H)‐arsenites (M1 = Li+, Na+, K+, Rb+, Cs+, Ca2+, Sr2+, Ba2+, Cd2+, Pb2+; M2 = Mg2+, Mn2+,3+, Fe2+,3+, Co2+, Ni2+, Cu2+, Zn2+) are less investigated. Up to now, only the structure of Pb3Mn(AsO3)2(AsO2OH) was described. The crystal structure of hydrothermally synthesized Na4Cd7(AsO3)6 was solved from the single‐crystal X‐ray diffraction data. Its trigonal crystal structure [space group R$\bar{3}$ , a = 9.5229(13), c = 19.258(4) Å, γ = 120°, V = 1512.5(5) Å3, Z = 3] represents a new structure type. The As atoms are arranged in monomeric (AsO3)3– units. The surroundings of the two crystallographically unique sodium atoms show trigonal antiprismatic coordination, and two mixed Cd/Na sites are remarkably unequal showing tetrahedral and octahedral coordinations. Despite the 3D connection of the AsO3 pyramids, (Cd,Na)Ox polyhedra and NaO6 antiprisms, a layer‐like arrangement of the Na atoms positioned in the hexagonal channels formed by CdO4 deformed tetrahedra and AsO3 pyramids in z = 0, 1/3, 2/3 is to be mentioned. These pseudo layers are interconnected to the 3D network by (Cd,Na)O6 octahedra. Raman spectra confirmed the presence of isolated AsO3 pyramids.  相似文献   

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