Effective crystal field for trivalent first transition row ions

In the present work the semiempirical effective crystal field (ECF) method previously designed for electronic structure calculations of transition metal complexes and utilizing non‐Hartree–Fock trial wave function and parameterized for complexes of doubly charged Cr²⁺, V²⁺, Mn²⁺, Fe²⁺, Co²⁺, and Ni²⁺ cations is extended to complexes of triply charged cations of 3d‐elements. With the parameters adjusted the ECF method is applied to calculations of ground states and low‐energy spectra of the d‐shells of fluoro‐, chloro‐, aqua‐, amino‐, and cyano‐complexes of the triply charged cations. Obtained total spin and symmetry of the ground states match the experimentally observed ones. Satisfactory agreement between the calculated and experimental d‐shell electronic transition energies is achieved as well. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

Hydrolytic ring opening reactions of anhydrides for first row transition metal dicarboxylate complexes

Ring opening reactions of 2,3-pyridine dicarboxylic anhydride are studied with hydrated salts of cobalt, nickel and zinc. The hydrated metal salts preferentially hydrolyze 2,3-pyridine dicarboxylic anhydride rather than causing esterification in methanol medium. Hydrolytic opening of 2,3-pyridine dicarboxylic anhydride by hydrated cobalt(II) acetate and nickel(II) acetate resulted in the corresponding chelate complexes of monodeprotonated 2,3-pyridine dicarboxylic acid. The reaction of copper acetate with pyromellitic dianhydride in the presence of 1,10-phenanthroline gives a dinuclear copper complex whereas a similar reaction with copper(II) chloride gives a mononuclear copper complex.     

Structure and photoluminescence of Mg-Al-Eu ternary hydrotalcite-like layered double hydroxides

A series of Mg-Al-Eu ternary hydrotalcite-like layered double hydroxides (LDHs), with Eu/Al atomic ratios of ∼0.06 and Mg/(Al+Eu) atomic ratios ranging from 1.3 to 4.0, were synthesized by a coprecipitation method. The Mg-Al-Eu ternary LDHs were investigated by various techniques. X-ray diffraction (XRD) results indicated that the crystallinity of the ternary LDHs was gradually improved with the increase of Mg²⁺/(Al³⁺+Eu³⁺) molar ratio from 1.3/1 to 4/1, and all the samples were a single phase corresponding to LDH. The photoluminescent (PL) spectra of the ternary Mg-Al-Eu LDHs were described by the well-known ⁵D₀-⁷F_J transition (J=1, 2, 3, 4) of Eu³⁺ ions with the strongest emission for J=2, suggesting that the host LDH was favorable to the emissions of Eu³⁺ ions. The asymmetry parameter (R) relevant to ⁵D₀-⁷F_J transition (J=1, 2) dependant of the atomic ratios of Mg²⁺/(Al³⁺+Eu³⁺) was discussed, and was consistent with the result of XRD.     

Theoretical study of the first transition row oxides and sulfides

Summary The first transition row oxides and sulfides are studied using several different levels of theory. The calculations show the bonding mechanism in the sulfides and oxides to be very similar. For the oxides, accurate experimental data allow the theoretical methods to be calibrated. The same level of theory is used to study the sulfides where there is far less experimental information. For ScO through MnO and CuO the coupled cluster singles and doubles technique including a perturbational estimate of the connected triple excitations [CCSD(T)] yields spectroscopic constants (_e, _e, andD ₀) in good agreement with experiment. The triple excitations are found to be very important in achieving this accuracy. For FeO to NiO, the self-consistent-field (SCF) approach yields orbitals that are localized on the metal or oxygen. This appears to cause problems for the single reference techniques; this is discussed in detail for NiO. The complete-active-space SCF/internally contracted averaged coupled pair functional approach (CASSCF/ICACPF) works well for FeO to NiO. The calculation of accurate dipole moments is found to be very difficult.     

Shape- and phase-controlled synthesis of monodisperse, single-crystalline ternary chalcogenide colloids through a convenient solution synthesis strategy

Colloidal, monodisperse, single-crystalline pyramidal CuInS2 and rectangular AgInS2 nanocrystals were successfully synthesized through a convenient and improved solvothermal process that uses hexadecylamine as a capping reagent. The crystal phase, morphology, crystal lattice, and chemical composition of the as-prepared products were characterized by using X-ray diffraction, transmission electron microscopy (TEM), high-resolution TEM, and energy dispersive X-ray spectroscopy. Results revealed that the as-synthesized CuInS2 colloid is in the tetragonal phase (size: 13-17 nm) and the AgInS2 in the orthorhombic structure (size: 17+/-0.5 nm). A possible shape evolution and crystal growth mechanism has been suggested for the formation of pyramidal CuInS2 and rectangular AgInS2 colloids. Control experiments indicated that the morphology- and/or phase-change of CuInS2 and orthorhombic AgInS2 colloids are temperature- and/or time-dependent. CuInS2 colloids absorb well in the range of visible light at room-temperature, indicating its potential application as a solar absorber. Two photoluminescence (PL) subbands at 1.938 and 2.384 eV in the PL spectra of CuInS2 colloids revealed that the recombination of the closest and the second closest donor-acceptor pairs within the CuInS2 lattice, in which the donor defect (Cui) occupies an interstitial position and the acceptor defect (VIn) resides at an adjacent cation site. In addition, the synthesis strategy developed in this study is convenient and inexpensive, and could also be used as a general process for the synthesis of other pure or doped ternary chalcogenides that require a controlled size (or shape). This process could be extended to the synthesis of other functional nanomaterials.     

The ternary metal mixed ligand complexes formed by benzimidazole and N, N-bis(2-hydroxyethyl) glycine

The stability constants of the ternary M(Bic)(Bzim)~ complexes, where M~(2 )=Cu~(2 ), Ni~(2 ) or Zn~(2 ), Bic~-=the anion of N, N-bis(2-hydroxyethyl) glycine and Bzim = benzimidazole, were determined by potentiometric pH titration in aqueous solution. One of them (M~(2 ) = Cu~(2 )) was also separately determined by spectrophotometry. The results show that these ternary complexes are stabler than expected on statistical grounds. The enhanced stability of the ternary M(Bic) (Bzim)~ complexes is attributed to the π_A-π_B cooperative effect between Bic~- and benzimidazole. Besides, compared with Cu(Bic) (Bzim)~ and Ni(Bic) (Bzim)~ , the ternary Zn(Bic)(Bzim)~ complex has relatively high stability. The crystal structure of [Cu(Bic)(Bzim)]ClO_4 was determined by single crystal X-ray diffraction techniques. The copper atom has a trigonal-bipyramidal geometry, the basal plane is formed by an oxygen atom of the carboxylato group and two hydroxyl oxygen atoms, the apical position is occupied by a nitrogen a     

Synthesis and Crystal Structure of a Heterometallic Trinuclear Ni/Ag/S Compound

A new tri-nuclear mixed metal thiolate complex [Ag(PPh3)2]2[Ni(edtO2)2] 1 has been synthesized and structurally characterized by single-crystal diffraction.The molecule has a crystallographic inversion centre occupied in the central Ni(II) atom and the two silver(I) atoms are related by the inversion centre.The unique structural feature is that one of thiolates of each edt ligand has been oxidized to sulfinate from the precursor [Ni(edt)2]2-to the neutral linear trinuclear complex.The crystal structure belongs to the monoclinic system,space group P21/n with a = 13.581(11),b = 12.239(9),c = 22.316(17) ,β = 103.08(2)o,V = 3613(5) 3,Z = 2,Mr = 1571.87,Dc = 1.445 g/cm3,μ = 1.046 mm-1,F(000) = 1604,T = 293(2) K,the final R = 0.0652 and wR = 0.1499 for 6776 observed reflections with I > 2σ(I).     

第一过渡系列金属元素单核水氧化催化剂的最新进展

水的氧化是光合作用的重要步骤,其提供用于二氧化碳固定的电子和质子,以及生物圈所必需的氧气.在将太阳能转换为化学能的人工光合作用中,设计合成高效稳定的水氧化催化剂是研究的关键.目前的催化体系主要是基于钌和铱等贵金属的金属氧化物纳米颗粒和多核金属配合物.基于钌和铱的单核催化体系近年来也得到了广泛的发展.最近几年,第一过渡系列金属元素单核水氧化催化剂快速得到重视.作为配合物中心原子,它们不仅具有丰富的氧化态,而且因相对充足的蕴藏和较低的开采冶炼成本,其具有钌和铱等贵金属不可比拟的重大优势和广阔的应用前景.本文总结了近几年第一过渡系列金属元素单核水氧化催化剂的进展,并在此基础上,简单讨论了氧—氧键的生成,为进一步设计新颖、具有高催化效率和高稳定性的单核水氧化催化剂提供了理论依据.     

First-principles study of ternary metal borocarbide compounds containing finite linear BC2 units

Electronic structures of the ternary metal borocarbide compounds Sc₂BC₂, Al₃BC₃ and Lu₃BC₃ containing linear BC₂ units are compared using density functional calculations. Results reveal a covalent bonding between the metallic matrix and the formally BC₂⁵⁻ nonmetal anions which is stronger for the aluminum compound than for the two others.     

New mixed tellurides of nickel and Group 13–14 metals Ni<Subscript>3−δ</Subscript>MTe<Subscript>2</Subscript> (M = Sn,In, Ga)

Three new mixed tellurides of nickel and group 13–14 metals Ni_3−δMTe₂ (M = Sn, In, Ga) were prepared by high-temperature ampoule synthesis and studied by powder X-ray diffraction analysis. The compound Ni_3−δSnTe₂ was also studied by single crystal X-ray diffraction analysis. The structural model of this phase and two analogs was described as consisting of layers with nickel-main group metal bonds confined from the above by tellurium atoms. The van der Waals gap formed through contacts between the tellurium atoms of neighboring layers is partially occupied by nickel atoms. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1879–1881, October, 2007.     

Stability constants of some bivalent first row transition metal chelates of dicarboxylic acids containing ether linkages

The stability constants of the Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+) and Zn(2+) complexes with four acids of the type HOOCCH(2)O(CH(2)CH(2)O)(n) CH(2)COOH (n = 0-3) are reported. For n = 0 the constants are in the Irving-Williams order, but not for n = 1-3.     

Solid State Synthesis and Crystal Structure of K3SI

1 INTRODUCTION The alkali metal chalcogenide halides have at- tracted considerable interests since last decades due to their abundant interesting structures and good properties with potential applications[1~8]. The type of M3QX (M = alkali metal, Q = chalcogenide; X = halide) compounds has been well studied. The known structure types of these compounds are only ternary alkali metal oxide halides and can be classified as the following species: 1) cubic anti-perovskite type, such as K3O…     

Comparative study of the synthesis of layered transition metal molybdates

Mixed metal oxides (MMOs) prepared by the mild thermal decomposition of layered double hydroxides (LDHs) differ in their reactivity on exposure to aqueous molybdate containing solutions. In this study, we investigate the reactivity of some T-Al containing MMOs (T=Co, Ni, Cu or Zn) towards the formation of layered transition metal molybdates (LTMs) possessing the general formula AT₂(OH)(MoO₄)₂·H₂O, where A=NH₄⁺, Na⁺ or K⁺. The phase selectivity of the reaction was studied with respect to the source of molybdate, the ratio of T to Mo and the reaction pH. LTMs were obtained on reaction of Cu-Al and Zn-Al containing MMOs with aqueous solutions of ammonium heptamolybdate. Rehydration of these oxides in the presence of sodium or potassium molybdate yielded a rehydrated LDH phase as the only crystalline product. The LTM products obtained by the rehydration of MMO precursors were compared with LTMs prepared by direct precipitation from the metal salts in order to study the influence of preparative route on their chemical and physical properties. Differences were noted in the composition, morphology and thermal properties of the resulting products.     

二维层状磷钒多金属氧酸盐的水热合成及晶体结构

利用中温水热技术合成了新型的磷矾铁酸盐(NH3CH2CH2NH3)4[FeV8O12(HPO4)6(PO4)2(H2O)2]·5H2O,通过元素分析、IR光谱、热重分析和X射线衍射确定了晶体结构.该晶体属单斜晶系,P21/n空间群,晶胞参数:a=1.4304(3)nm,b=1.0145(2)nm,c=1.8356(4)nm,β=90.15(3)°,V=2.6637(9)nm3,Z=2,最终偏差因子R1=0.0631,wR2=0.1874.     

Recent advancements in the anticancer potentials of first row transition metal complexes

The frequently severe effects of currently utilized platinum-based complexes have prompted researchers to develop less toxic transition metal based anticancer drugs. Transition metal complexes have recently gained considerable attention as promising anticancer agents due to their efficient drug design and fast optimisation. Some transition metal complexes displayed better anticancer activity than cis-platin. This led to the transition metal complexes for clinical application of chemotherapeutic drugs for cancer therapy. Cytotoxicity of the complexes has been evaluated on the basis of their IC₅₀ values. In this review, we have focussed on recent findings about the anticancer mechanism of action of first row transition metal complexes during the last ten years.     

Electronic structure of first and second row atoms under harmonic confinement

Atoms under pressure undergo a number of modifications of their electronic structure. Good examples are the spontaneous ionization, stabilization of excited-state configurations, and contraction of atomic-shells. In this work, we study the effects of confinement with harmonic potentials on the electronic structure of atoms from H to Ne. Dynamic and static correlation is taken into account with coupled cluster with single and double excitations and CASSCF calculations. Because the strength of harmonic confinement cannot be translated into pressure, we envisioned a “calibration” method to transform confinement into pressure. We focused on the effect of confinement on: (a) changes of electron distribution and localization within the K and L shells, (b) confinement-induced ionization pressure, (c) level crossing of electronic states, and (d) correlation energy. We found that contraction of valence and core-shells are not negligible and that the use of standard pseudopotentials might be not adequate to study solids under extreme pressures. The critical pressure at which atoms ionize follows a periodic trend, and it ranges from 28 GPa for Li to 10.8 TPa for Ne. In Li and Be, pressure induces mixing of the ground state configuration with excited states. At high pressure, the ground states of Li and Be become a doublet and a triplet with configurations 1s²2p and 1s²2s2p, respectively, which could change the chemistry of Be. Finally, it is observed that atoms with fewer electrons correlation increases, but for atoms with more electrons, the increasing of kinetic energy dominates over electron correlation.     

无机-有机杂化层状锑硫化合物的溶剂热合成与结构

用溶剂热法合成了有机杂化层状锑硫化合物[C3H7NH3]2Sb4S7,并利用单晶X-射线衍射测定了其晶体结构。该化合物为三斜晶系,Pī空间群。晶胞参数:a=7.0098(10),b=11.9710(14),c=13.6685(17),α=115.244(6)°,β=98.671(9)°,γ=92.413(13),°V=1018.3(2)3,Z=2,Mr=831.71 g.mol-1,(=5.984 mm-1,F(000)=772,偏差因子R1=0.0334,wR2=0.0766。该化合物由质子化正丙胺离子[C3H7NH3] 和二维阴离子[Sb4S7]n2n-组成,[Sb4S7]n2n-二维离子由3个SbS3三角锥和1个SbS4变形四面体单元连接而成,[C3H7NH3] 离子位于无机阴离子层之间,形成三明治夹心式结构,[C3H7NH3] 的-NH3 基团与无机阴离子层的S原子形成N-H…S氢键作用。     

Synthesis and Single Crystal Structure of RbEr_2Cu_3Se_5

1 INTRODUCTION Halide fluxes are excellent media for growing single crystals of chalcogenides[1~3]. It is well known that during the single crystal growth via flux methods, occasional inclusion of the flux elements in the structure leads to the formation of new phases[4~9]. Several rare earth chalcogenides have been prepared through such reactive halid flux methods[4~9]. Thus we used RbCl as reactive flux to explore a new quaternary selenide by the reaction of ErCuSe precursor with Rb…     

Relative stabilities of layered perovskite and pyrochlore structures in transition metal oxides containing trivalent bismuth

In order to investigate the factors determining the relative stabilities of layered perovskite and pyrochlore structures of transition metal oxides containing trivalent bismuth, several ternary and quaternary oxides have been investigated. While d⁰ cations stabilize the layered perovskite structure, cations containing partially-filled d orbitals (which suppress ferroelectric distortion of MO₆ octahedra) seem to favor pyrochlore-related structures. Thus, the vanadium analogue of the layered perovskite Bi₄Ti₃O₁₂ cannot be prepared; instead the composition consists of a mixture of pyrochlore-type Bi_1.33V₂O₆, Bi₂O₃, and Bi metal. The distortion of Bi_1.33V₂O₆ to orthorhombic symmetry is probably due to an ordering of anion vacancies in the pyrochlore structure. None of the other pyrochlores investigated, Bi₂NbCrO₇, Bi₂NbFeO₇, TlBiM₂O₇ (M = Nb, Ta), shows evidence for cation ordering in the X-Ray diffraction patterns, as indeed established by structure refinement of TlBiNb₂O₇.     

Structure, energetics, and bonding of first row transition metal pentazolato complexes: a DFT study

Quantum chemical calculations with gradient-corrected (B3LYP) density functional theory for the mono- and bispentazolato complexes of the first row transition metals (V, Cr, Mn, Fe, Co, and Ni), the all-nitrogen counterparts of metallocenes, were performed, and their stability was investigated. All possible bonding modes (e.g. eta1, eta2, eta3, and eta5) of the pentazolato ligand to the transition metals have been examined. The transition metal pentazolato complexes are predicted to be strongly bound molecules. The computed total bond dissociation enthalpies that yield free transition metal atoms in their ground states and the free pentazolato ligands were found in the range of 122.0-201.9 (3.7-102.3) kcal mol(-1) for the bispentazolato (monopentazolato) complexes, while those yielding M2+ and anionic pentazolato ligands were found in the range of 473.2-516.7 (273.6-353.5) kcal mol(-1). The electronic ground states of azametallocenes along with their spectroscopic properties (IR, NMR, and UV-vis) obtained in a consistent manner across the first transition metal series provide means for discussion of their electronic and bonding properties, the identification of the respective azametallocenes, and future laboratory studies. Finally, exploring synthetic routes to azametallocenes it was found that a [2 + 3] cycloaddition of dinitrogen to a coordinated azide ligand with nickel(II) does not seem to provide a promising synthetic route for transition metal pentazolato complexes while the oxidative addition of phenylpentazole and fluoropentazole to Ni(0) bisphosphane complexes merits attention for the experimentalists.