Density functional investigations of endohedral metallofullerenes TM@C24 (TM = Mn,Fe, Co,Ni, Cu,and Zn)

The theoretical investigations on TM@C₂₄ (TM = Mn, Fe, Co, Ni, Cu, and Zn) with different spin configurations have been performed by using the hybrid DFT‐B3PW91 functional in conjunction with 6‐31G(d) basis sets. The results show that the ground states of Fe@C₂₄ and Ni@C₂₄ are their spin triplet states, whereas the ground state of Co@C₂₄ is spin quartet state. Moreover, three Fe@C₂₄ isomers are favorable in energy. The HOMO and LUMO of Zn@C₂₄ indicates that there is no hybridization between Zn atomic orbitals and the C₂₄ cage orbitals. Natural population analysis shows that the charges always transfer from the TM atoms to the C₂₄ cage. In going from isolated TM atom to TM@C₂₄, the occupation of the 4s orbital is strongly reduced. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

K_2NiF_4型结构的A_（2－x）Sr_xBO_4（A＝La，Dy，B＝Mn，Fe，Co，Ni）希土复合氧化物的合成

以典型的轻希土镧和重希上镝及碱土金属锶作为Ａ位离子，以过渡金属锰、铁、钴、镍作为Ｂ位离子，合成了Ｋ２ＮｉＦ４型结构的Ａ２－ｘＳｒｘＢＯ４希土复合氧化物．采用粉末Ｘ射线衍射技术考察了反应条件等因素对生成Ｋ２ＮｉＦ４型四方（Ｔ）结构相的影响．实验结果表明，四方结构的形成不仅与几何因素有关，而且与各组分的物理化学性质有关．各个不同的组成，生成四方相的温度范围也有所不同．适当地提高反应温度以及延长灼烧时间总是有利于高结晶态的Ｋ２ＮｉＦ４型结构相的形成．值得注意的是，过高的合成反应温度反而会引起四方结构的不稳定性以致破坏．     

Synthesis, crystal structure and magnetic properties of novel heterobimetallic malonate-bridged MIIReIV complexes (M = Mn, Fe, Co and Ni)

Five novel ReIV-MII bimetallic complexes of formula [ReCl4(mu-mal)M(dmphen)2].MeCN [M = Co (1), Fe (2) and Ni (3)], [ReCl4(mu-mal)Ni(dmphen)(MeCN)2(H2O)].(MeCN)0.5(H2O)0.5 (4), and [ReCl4(mu-mal)Mn(dmphen)(H2O)2].dmphen.MeCN.H2O (5) (mal = malonate dianion, dmphen = 2,9-dimethyl-1,10-phenanthroline) have been synthesized, and the structures of 1, 2, 4, and 5 determined by single-crystal X-ray diffraction. The structures of 1 and 2 consist of neutral [ReCl4(mu-mal)M(dmphen)2] dinuclear units where the metal ions are linked through a malonate ligand which adopts simultaneously the bidentate (at ReIV) and monodentate (at MII) coordination modes. The bridging carboxylate-malonate group in them exhibits the anti-syn conformation. The rhenium atom is six-coordinated with four chloro atoms and two carboxylate-oxygens from a bidentate malonate group in a distorted octahedral environment. The M atom is five-coordinated being surrounded by four nitrogen atoms of two bidentate dmphen ligands and one oxygen atom of the malonato ligand. There are also ReIV(mu-mal)NiII dinuclear units in 4 with the same type of bridge, but the nickel atom is six-coordinated with one bidentate dmphen, two molecules of acetonitrile and one water molecule as peripheral ligands. Compound 5 is a neutral chain compound with regular alternating rhenium(IV) and manganese(II) ions. The [ReCl4(mal)]2- units in each chain act as bismonodenate ligands through two carboxylate-oxygen atoms toward [Mn(dmphen)(H2O)2]2+ entities. Variable-temperature magnetic measurements of 1-5 in the temperature range 2.0-300 K show the occurrence of weak antiferromagnetic interactions which are rationalized on the basis of the structural knowledge and simple orbital considerations. Very noticeable is compound 5, a ferrimagnetic chain with regular alternating ReIV and MnII cations.     

The structural,mechanical, and thermodynamic properties of B2-type TMZr (TM = Ru,Mo, Rh,Os, and Re) compounds from first-principles calculations

The B2-type cubic Zr-based compounds are attractive advanced high-temperature materials because of the strong and symmetrical bonds. However, the mechanical and thermodynamic properties of the B2-type cubic Zr-based compounds are not well understood. Here, we use the first-principles calculations to investigate the structural, elastic modulus, ductility, and thermodynamic properties of TMZr (TM = Ru, Mo, Rh, Os, and Re) compounds. Two novel TMZr compounds, MoZr and ReZr, are first predicted by using the phonon dispersion and formation enthalpy, respectively. The results show that the B2-type TMZr compounds not only exhibit high elastic modulus but also show better ductility due to the symmetrical TM-Zr metallic bonds. In particular, the calculated elastic modulus of OsZr is larger than that of the other four TMZr compounds, indicating that the OsZr shows the strongest deformation resistance in five TMZr compounds. The calculated Θ _D of RuZr is 328 K, which is larger than that of the other four TMZr compounds. The calculated phonon density of state shows that the high-temperature thermodynamic properties of TMZr derive from the vibration of Zr atom. Therefore, our work predicts that the B2-type OsZr is an attractive high-temperature structural material.     

Hydrogenation characteristics of the hyperstoichiometric ZrCrFeTx system (T = Mn,Fe, Co,Ni, or Cu)

The formation and characteristics of the hydride of ZrCrFeT_x (T = Mn, Fe, Co, Ni, or Cu and x = 0.8) were studied at various temperatures and in the pressure range up to ～60 atm. The hydrogen vapor pressure of the ZrCrFeH system is raised approximately 10- to 400-fold by the addition of excess d-element or Cu to the ZrCrFe lattice. The equilibrium vapor pressure of ZrCrFeCo_0.8H is unusually high relative to the other quaternary systems and is consistent with the observed unit cell dimensions. This pronounced effect suggests that the Co has a striking influence on the ZrCrFe band structure. The enthalpy and entropy of dehydrogenation, ranging between 19.4 and 32 kJ(mole H₂)^?1 and 77.2 and 100 J(kmole H₂)^?1, are significantly lower than that of the ZrCrFeH. The high effective entropies of the hydride (high configurational entropy of H in the lattice) is attributed to extensive hydrogen disorder in the ZrCrFeT_0.8 lattice. The kinetics of hydride formation and decomposition are extremely fast. The favorable thermodynamic features and rapid kinetics make these substances rather attractive for practical applications.     

The interaction of alkaline solutions of potassium borohydride with LaNi4.5M0.5 (M = Ni,Mn, Cr,Co, Fe,Cu, Al) intermetallic compounds

The behavior of LaNi_4.5M_0.5 (M = Ni, Mn, Cc Co, Fe, Cu, Al) interinctallic compounds (IMC) in alkaline solutions of KBH₄ (0.1; 1.0; 4.0 mol L^–1 KOH) Was investigated in the temperature range 298–318 K. The catalytic hydrolysis of KBH₄ is zero order with respect to KBH₄ and not order with respect to IMC. Activation energies of the catalytic hydrolysis of KBH₄ in the presence of' IMC are in the range of 60–65 U mol^–1. The rate of hydrolysis of KBH₄ increases with the concentration of the KOH solution. The hydrogenation of LaNi_4.5M_0.5 in alkaline solutions of KBH₄ yields -hybride phases for M = Min, Cr, Co, Cu, Al and -hybride phases for M = Ni, Fe.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1632–1635, July, 1996.     

Thermodynamic Dissociation Constants for [MPy4(NO3)2]*2Py Clathrates (M=Mn,Co, Ni,Cu)

Abstract

Stoichiometry and thermodynamic parameters of the title clathrates dissociation have been studied with thermoanalytical and strain method techniques. The [MPy₄(NO₃)₂]^*2Py (M = Mn, Co, Ni) clathrates dissociate with collapsing clathrate porous phase and destruction of the host complex to give the respective tripyridine complexes and gaseous pyridine. The [CuPy₄(NO₃)₂]^*2Py dissociates with collapsing clathrate phase but giving the host [CuPy₄(NO₃)₂] complex as individual phase, with the tripyridine complex forming in further course of decomposition. The comparison of the thermodynamic dissociation parameters for the [MPy₄(NO₃)₂]^*2Py series with M = Mn, Co, Ni, Cu, Zn and Cd shows that the differences in the stability of the compounds do not correlate with structural parameters of the clathrates but depend on the nature of the metal cation in the host complex. Thermodynamic stability of these clathrate phases follows the general sequence of stabilty for complexes of the 3d transition metals known as Irwing-Williams sequence: Mn<Fe<Co<Ni<Cu>Zn. These results disclose the main issue of instability of the [MPy₄(NO₃)₂]^*2Py clathrates as instability of the respective host complexes.     

四元Mg0.9Ti0.1Ni0.9X0.1(X=Mn,Zn,Co,Fe)系列合金的制备及性能研究

用机械合金化法合成了Mg0·9Ti0·1Ni0·9X0·1(X=Mn,Zn,Co,Fe)系列合金.X射线衍射(XRD)结构分析表明,用X部分替代Ni后,促进了Mg0·9Ti0·1Ni合金的非晶化过程.用Co和Fe部分替代Ni提高了合金的放电容量,但却降低了合金的循环稳定性.用Zn和Mn部分替代Ni提高了合金电极的循环寿命,尤其是Mg0·9Ti0·1Ni0·9Zn0·1合金电极经10个充放电循环后,其放电容量仍可达到313·8mA·h/g.对添加Co后的合金进行p-c-T测试发现,Mg0·9Ti0·1Ni0·9Co0·1合金的吸放氢容量明显比Mg0·9Ti0·1Ni合金高,这与电化学所测到的结果一致.     

Magnetic ordering and spin structure in Ca-bearing clinopyroxenes CaM(Si, Ge)2O6, M=Fe, Ni, Co, Mn

The compounds CaFeSi₂O₆ (hedenbergite), CaNiGe₂O₆, CaCoGe₂O₆ and CaMnGe₂O₆ have been synthesized by hydrothermal or ceramic sintering techniques and were subsequently characterized by SQUID magnetometry and powder neutron diffraction in order to determine the magnetic properties and the spin structure at low temperature. All four compounds reveal the well-known clinopyroxene structure-type with monoclinic symmetry, space group C2/c, Z=4 at all temperatures investigated. Below 35 K hedenbergite shows a ferromagnetic (FM) coupling of spins within the infinite M1 chains of edge-sharing octahedra. This FM coupling dominates an antiferromagnetic (AFM) coupling between neighbouring chains. The magnetic moments lie within the a-c plane and form an angle of 43° with the crystallographic a-axis. Magnetic ordering in CaFeSi₂O₆ causes significant discontinuities in lattice parameters, Fe-O bond lengths and interatomic Fe-Fe distances through the magnetic phase transition, which could be detected from the Rietveld refinements of powder neutron diffraction data. CaCoGe₂O₆ and CaNiGe₂O₆ show magnetic ordering below 18 K, the spin structures are similar to the one in hedenbergite with an FM coupling within and an AFM coupling of spins between the M1 chains. The moments lie within the a-c plane. The paramagnetic Curie temperature, however, decreases from CaFeSi₂O₆ (+40.2 K) to CaCoGe₂O₆ (+20.1 K) and CaNiGe₂O₆ (−13.4 K), suggesting an altered interplay between the concurring AFM and FM interaction in and between the M1 chains. CaMnGe₂O₆ finally shows an AFM ordering below 11 K. Here the magnetic moments are mainly oriented along the a-axis with a small tilt out from the a-c plane.     

Encapsulation of transition metals in aluminum nitride fullerene: TM@(AlN)12 (TM = Ti, Mn, Fe, Co, and Ni)

The structure and stability of endohedral TM@(AlN)₁₂ (TM = Ti, Mn, Fe, Co, Ni) complexes are studied at the level of density functional theory. It is found that complexes with TM = Mn, Fe, and Ni are energy minimum structures with TM at the cage center in T _h symmetry, while those with TM = Ti and Co have more negative inclusion energies and the off-centered structures with TM placed towards one hexagon face in C ₁ symmetry. The calculations predict that the HOMO and LUMO energy gap of TM@(AlN)₁₂ differs from those of the (AlN)₁₂ cage and a free TM atom. The amount of charge that is transferred from the encapsulated guests to the cage increases with the atomic radius. The electronic and magnetic properties of TM@(AlN)₁₂ are discussed.     

Heterotrimetallic oxalato-bridged ReIV2MII complexes (M=Mn, Co, Ni, Cu): synthesis, crystal structure, and magnetic properties

The use of the (NBu4)2[ReIVCl4(ox)] mononuclear species as a ligand toward divalent first row transition metal ions in the presence of imidazole affords the new trinuclear compounds of formula (NBu4)2[{ReIVCl4(mu-ox)}2MII(Him)2] [NBu4+=tetra-n-butylammonium cation, ox=oxalate dianion, Him=imidazole; M=Mn (1), Co (2), Ni (3), Cu (4)] whose preparation, crystal structures, and magnetic properties are reported. 1-4 are isostructural complexes which are made up of discrete trinuclear [{ReIVCl4(mu-ox)}2MII(Him)2]2- anions and bulky NBu4+ cations. The Re and M atoms exhibit somewhat distorted octahedral surroundings which are built by four chloro and two oxalate oxygens (Re) and two imidazole nitrogen and four oxalate oxygen atoms (M), the central M atom being linked to the two peripheral Re atoms through bis-bidentate oxalate. The values of the Re...M separation across bridging oxalate vary in the range 5.646(2) (M=Ni) to 5.794(2) A (M=Mn). Magnetic susceptibility measurements on polycrystalline samples of 1-4 in the temperature range 1.9-300 K show the occurrence of significant intramolecular antiferro- (1) and ferromagnetic (2-4) interactions. The nature and magnitude of the magnetic coupling in 1-4 are qualitatively understood through orbital symmetry considerations.     

Heterobimetallic oxalato-bridged M(II)Re(IV) complexes (M = Mn,Fe, Co,Ni): synthesis,crystal structure,and magnetic properties

Four rhenium(IV)-M(II) bimetallic complexes of formula [ReCl(4)(mu-ox)M(dmphen)(2)].CH(3)CN with M = Mn (1), Fe (2), Co (3), and Ni (4) (ox = oxalate anion, dmphen = 2,9-dimethyl-1,10-phenanthroline) have been synthesized and the crystal structures of 1 and 3 determined by single-crystal X-ray diffraction. 1 and 3 are isostructural and crystallize in the monoclinic system, space group P2(1)/c, with a = 16.008(4) A, b = 12.729(2) A, c = 18.909(5) A, beta = 112.70(2) degrees, and Z = 4 for 1 and a = 15.998(4) A, b = 12.665(2) A, c = 18.693(5) A, beta = 112.33(2) degrees, and Z = 4, for 3. The structure of 1 and 3 is made up of neutral [ReCl(4)(mu-ox)M(dmphen)(2)] bimetallic units (M = Mn (1), Co (3)) and acetonitrile molecules of crystallization. M(II) and Re(IV) metal ions exhibit distorted octahedral coordination geometries being bridged by a bis(bidentate) oxalato ligand. The magnetic behavior of 1-4 has been investigated over the temperature range 2.0-300 K. A very weak antiferromagnetic coupling between Re(IV) and Mn(II) occurs in 1 (J = -0.1 cm(-)(1)), whereas a significant ferromagnetic interaction between Re(IV) and M(II) is observed in 2-4 [J = +2.8 (2), +5.2 (3), and +5.9 cm(-)(1) (4)].     

Heterometallic M/Mn (M=Cu, Co, Zn) acetate complexes as precursors for binary oxides

A facile one-pot procedure, or so-called “direct synthesis,” was used to prepare the novel heterometallic complexes [M₂Mn(OAc)₆(bpy)₂], where M=Cu (1), Co (2), Zn (3), bpy=2,2′-bipyridyl, with high yields via oxidative dissolution of pure metals in a liquid phase. The complexes were characterized by an elemental analysis, single crystal X-ray diffraction method and FTIR. These complexes are proposed as precursors, whose thermal degradation may lead to the formation of solids possessing nano- to microsize levels of dispersity. The thermal behavior of the complexes obtained was studied by thermal analysis (TG/DTA/DTG) in both air and N₂ and also by TPD mass-spectrometry in vacuo. The FTIR, X-ray powder diffraction (PXRD) and thermoanalytical data were used for the identification of the solid products of thermal degradation. The morphology and microstructure of the solid residues were analyzed, using scanning electron microscopy with energy dispersive X-ray microanalysis (SEM/EDX) at mkm and sub-micro levels.     

MC_2O_4(M=Mn、Fe、Co、Ni、Cu、Zn)的热力学及其热分析动力学

用DSC、TGA技术分别在N2气氛和O2气氛下对MC2O4(M=Mn、Fe、Co、Ni、Cu、Zn)的脱水和分解过程作了热力学和动力学的研究.在N2气氛下,MC2O4·2H2O(M=Mn、Fe、Co、Ni、Zn)脱水温度Tde和脱水焓!deHm随原子序数Zre递增呈现明显的“二分组效应”;!deHm在(96.46±7.00)kJ·mol-1范围内波动;MC2O4·2H2O(M=Mn、Fe、Ni)的分解温度Td随原子序数递增呈现良好的线性关系;且各草酸盐分解得到氧化物(CuC2O4生成Cu、CuO混合物)时,MC2O4(M=Co、Ni、Cu)分解焓随原子序数增大也存在良好的线性关系.各草酸盐除NiC2O4·2H2O脱水过程和FeC2O4分解过程外,其余各过程机理函数均为随机成核和随后成长型.     

MC2O4(M=Mn、Fe、Co、Ni、Cu、Zn)的热力学及其热分析动力学

用DSC、TGA技术分别在N₂气氛和O₂气氛下对MC₂O₄(M=Mn、Fe、Co、Ni、Cu、Zn)的脱水和分解过程作了热力学和动力学的研究. 在N₂气氛下, MC₂O₄•2H₂O(M=Mn、Fe、Co、Ni、Zn)脱水温度Tde和脱水焓ΔdeHm随原子序数Zre递增呈现明显的“二分组效应”；ΔdeHm在(96.46±7.00) kJ•mol^-1范围内波动；MC₂O₄•2H₂O (M=Mn、Fe、Ni)的分解温度Td随原子序数递增呈现良好的线性关系；且各草酸盐分解得到氧化物(CuC₂O₄生成Cu、CuO混合物)时, MC₂O₄(M=Co、Ni、Cu) 分解焓随原子序数增大也存在良好的线性关系. 各草酸盐除NiC₂O₄•2H₂O脱水过程和FeC₂O₄分解过程外, 其余各过程机理函数均为随机成核和随后成长型.     

Catalytic reduction of NO_x by CO on hydro-talcites-derived mixed oxides Co AIM and MgAlM (M = Cr, Mn, Fe, Co, Ni, Cu)

Two series of mixed oxides, CoAlM and MgAlM (M= Cr, Mn, Fe, Co, Ni, Cu) , were prepared by calcining their corresponding hydrotalcite-like compounds (HTLc) . The ratio of Mg: Al: M (or Co: Al: M) was 3:1:1. The catalytic activity of all samples for the reaction of NO CO was investigated. The results showed that the activity of CoAlM was much higher than that of MgAlM. The structure and the property of redox were characterized by XRD and H2-TPR. The results indicated that only MgO phase was observed after calcining MgAlM hydrotalcites, and the transition metals became more stable. The spinel-like phase appeared in all of CoAlM samples after the calcination, and the transition metals were changed to be more active, and easily reduced . The activities of three series of mixed oxides CoAlCu obtained from different preparation methods, different ratio of Co:Al:Cu and at different calcination temperatures, were studied in detail for proposing the mechanism of reaction. The ability of adsorption of NO and CO     

Magnetic Susceptibilities of ThM2X2 Compounds (M = Cr,Mn, Fe,Co, Ni and Cu; X = Si and Ge)

Magnetic susceptibilities of a series of ternary intermetallic compounds of the general composition ThM₂X₂(M = Cr, Mn, Fe, Co, Ni and Cu; X = Si and Ge) were determined by means of FARADAY method in the temperature interval 100–570°K. The results confirm the previously proposed magnetic behaviour of these compounds, based on the observation of the basic crystallographic parameters as a function of the atomic number of the transition metal element. The compounds were found to be alternatively ferromagnetics and antiferromagnetics depending on the atomic number of the transition metal atom.     

Syntheses,structures and magnetic properties of Mn(II) containing 3D polymeric networks

Two novel 3D coordination polymers {[Mn(aip)(DMF)]}_n, CPO-9, and {[Mn₃(Hatp)₂(atp)₂](H₂O)₂(DEF)₄}_n CPO-10 (aip = 5-aminoisophthalate, atp = 2-aminoterephthalate, DMF = dimethylformamide, DEF = diethylformamide) have been synthesized by solvothermal methods. Their properties have been studied by single-crystal X-ray diffraction, thermogravimetric analysis, high-temperature powder X-ray diffraction and magnetic susceptibility measurements. The crystal structure of CPO-9 is based on infinite chains of carboxylato-bridged five-coordinated Mn(II) ions that are crosslinked via the aip ligands to form a 3D structure. CPO-10 is based on linear trinuclear building units of carboxylato-bridged octahedral Mn(II) ions that are crosslinked by the atp ligands into a 3D structure. Both compounds have 1D channels that contain solvent molecules. The solvent accessible void volume for CPO-10 is 51.9% of the unit cell volume. For both compounds, however, the solvent molecules cannot be removed without the collapse of the structures into amorphous phases at 250 °C. The magnetic susceptibility measurements indicate antiferromagnetic couplings between the Mn(II) ions in both compounds. The magnetic data have been fitted using theoretical approaches.     

Metal‐Organic Niccolite: Synthesis,Structures, Phase Transition,and Magnetic Properties of [CH3NH2(CH2)2NH2CH3][M2(HCOO)6] (M=divalent Mn,Fe, Co,Ni, Cu and Zn)

We report the synthesis, crystal structures, thermal and magnetic characterizations of a family of metal‐organic frameworks adopting the niccolite (NiAs) structure, [dmenH₂²⁺][M₂(HCOO)₆²⁻] (dmen=N,N′‐dimethylethylenediamine; M=divalent Mn, 1Mn ; Fe, 2Fe ; Co, 3Co ; Ni, 4Ni ; Cu, 5Cu ; and Zn, 6Zn ). The compounds could be synthesized by either a diffusion method or directly mixing reactants in methanol or methanol–water mixed solvents. The five members, 1Mn , 2Fe , 3Co , 4Ni , and 6Zn are isostructural and crystallize in the trigonal space group P 1c, while 5Cu crystallizes in C2/c. In the structures, the octahedrally coordinated metal ions are connected by anti–anti formate bridges, thus forming the anionic NiAs‐type frameworks of [M₂(HCOO)₆²⁻], with dmenH₂²⁺ located in the cavities of the frameworks. Owing to the Jahn–Teller effect of the Cu²⁺ ion, the 3D framework of 5Cu consists of zigzag Cu‐formate chains with Cu OCHO Cu connections through short basal Cu O bonds, further linked by the long axial Cu O bonds. 6Zn exhibits a phase transition probably as a result of the order–disorder transition of the dmenH₂²⁺ cation around 300 K, confirmed by differential scanning calorimetry and single crystal X‐ray diffraction patterns under different temperatures. Magnetic investigation reveals that the four magnetic members, 1Mn , 2Fe , 3Co , and 4Ni , display spin‐canted antiferromagnetism, with a Néel temperature of 8.6 K, 19.8 K, 16.4 K, and 33.7 K, respectively. The Mn, Fe, and Ni members show spin‐flop transitions below 50 kOe. 2Fe possesses a large hysteresis loop with a large coercive field of 10.8 kOe. The Cu member, 5Cu , shows overall antiferromagnetism (both inter‐ and intra‐chains) with low‐dimensional characteristics.