Metal–Oleate Complex?Derived Bimetallic Oxides Nanoparticles Encapsulated in 3D Graphene Networks as Anodes for Efficient Lithium Storage with Pseudocapacitance

In this manuscript, we have demonstrated the delicate design and synthesis of bimetallic oxides nanoparticles derived from metal–oleate complex embedded in 3D graphene networks(MnO/CoMn_2O_4  GN), as an anode material for lithium ion batteries. The novel synthesis of the MnO/CoMn_2O_4  GN consists of thermal decomposition of metal–oleate complex containing cobalt and manganese metals and oleate ligand, forming bimetallic oxides nanoparticles, followed by a selfassembly route with reduced graphene oxides. The MnO/CoMn_2O_4  GN composite, with a unique architecture of bimetallic oxides nanoparticles encapsulated in 3D graphene networks, rationally integrates several benefits including shortening the di usion path of Li^+ ions, improving electrical conductivity and mitigating volume variation during cycling. Studies show that the electrochemical reaction processes of MnO/Co Mn_2O_4  GN electrodes are dominated by the pseudocapacitive behavior, leading to fast Li^+ charge/discharge reactions. As a result, the MnO/CoMn_2O_4  GN manifests high initial specific capacity, stable cycling performance, and excellent rate capability.

CATALYTIC BEHAVIOR OF SILICA-SUPPORTED POLY-γ- AMINOPROPYL- SILOXANE-Co-Ru BIMETALLIC COMPLEX FOR THE HYDROFORMYLATION OF CYCLOHEXENE

The cobalt and ruthenium bimetallic complex of poly-γ-amino-propylsiloxane( abbr. as Si-CH_2-Co-Ru) was prepared, and it was found that it can catalyze the hydroformylation of cyclobexene effectively with the conversion amounting to over 90%. Cyclohexanecarboxaldehyde was first formed in the hydroformylation, and then further hydrogenated to form cylcohexanemethanol. The coversion was affected obviously by the Co/Ru ratio.When Co/Ru molar ratio was 100-150, i.e. in the very low content of noble metal Ru, the catalytic activity of Si-NH_2 -Co-Ru was also very high. The product composition was affected by CO/H_2 ratio in the reaction gas. Aldehyde can be got high selectively by controlling CO/H_2 ratio. Compared with other catalyst system, the Si-NH_2-Co-Ru catalyst has higher catalytic activity and efficiency with very low Ru/Co ratio. The total turnover number was more than 28,800 (based on the amount of ruthenium used).

STUDY ON POLYMER-Ru-Co BIMETALLIC COMPLEXES CATALYSTS Ⅱ.X-RAY PHOTOELECTRON SPECTROSCOPIC ANALYSIS

Polymer Ru-Co bimetallic complexes have been examined by X-ray photoelectron spectroscopy.The catalyst is highly active only when the mole ratio of Co/Ru is 4: 3. The activity of catalysts does not depend on the total Co/Ru ratio, but on the surface stoichiometry of Co and Ru. When the relative intensities of Co_2_p and Ru_(3d) of XPS peaks are close to each other and both are high,the catalyst exhibits its maximum activity The mechanism ofcatalytic hydroformylation has been discussed.

STUDY ON POLYMER—Ru-Co—BIMETALLIC COMPLEXES CATALYSTS Ⅰ. SYNTHESIS OF CATALYSTS AND THEIR USE FOR THE HYDROFORMYLATION

Six kinds of polymer ligands, supported on SiO_2, containing coordinating atoms P, S and N respectively, have been synthesized. The Ru(Ⅲ)-Co(Ⅱ) bimetallic complexes of these polymer ligands have been obtained and examined as catalysts for the hydroformylation of cyclohexene. The effects of reaction temperature, pressure and Co/Ru ratio etc. on the activities of catalysts were investigated in detail. The catalysts are all polymer-noncarbonyl-metal complexes, easily to be prepared, active and stable. From the experimental results it can be suggested that under reaction conditions such polymer-noncarbonyl-metal complexes convert 'in situ' to polymer-carbonyl-metal complexes, thus become active catalysts. The course of this conversion is supposed as a preliminary approach.

Synthesis and Molecular Structure of A Bimetallic Salen Complex Containing Zn and La: A Disordered Nitrate Group Dancing between Two Metal Centers

A new bimetallic complex containing Zn and La was prepared from a salen ligand possessing methoxyl groups at the 3, 3′-positions. The structural feature is that one of nitrate groups is disordered and displaced between two metal centers. Crystal system: Triclinic space group:P-1, Z=2. a=0.82714(17) nm, b=1.3484(3) (1) nm, and c=1 3898(3) (1) nm, α=79.89(3)°, β=76.67(3)°, and γ=72.43(3)°. V=1 428 6(5) nm3, Dx=1.812 g·cm-3. (Δρ)max=1 510×10-3 enm3, (Δρ)min=-1.503×10-3 enm3. Accordingly, two water molecules occupy the metal centers in the apical positions via the syn-geometry.

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ce(DMSO)_4(H_2O)_3Fe(CN)_6]·H_2O and [La(DMSO)_4(H_2O)_3Co(CN)_6]·H_2O(DMSO = Dimethylsulfoxide)

Two new bimetallic cyano-bridged complexes [Ce（DMSO）4（H2O）3Fe（CN）6]·H2O 1 and [La（DMSO）4（H20）3Co（CN）6].H20 2 have been prepared by the ball milling reaction method and structurally characterized by X-ray single-crystal structure analyses. Crystallographic data for 1： C14H32CeFeN6O8S4, Mr= 736.67, monoclinic, space group P2 1/n, a = 14.952（1）, b = 13.7276（9）, c = 15.392（1） A, β= 108.288（1）°, V = 2999.6（4） A3, Z = 4, Dc= 1.631 g/cm^3, g = 2.304 mm^-1, F（000） = 1480, R = 0.0593 and wR = 0.1611; and those for 2： C14H32CoLaN6O8S4, Mr=738.54, monoclinic, space group P21/n, a = 14.945（3）, b = 13.731（3）, c = 15.300（3） A, β= 107.806（1）°, V= 2989.3（11） A^3, Z= 4, Dc = 1.641 g/cm^3, μ = 2.288 mm^-1, F（000） = 1480, R = 0.0383 and wR = 0.1132. In both complexes the lanthanide ion is eight-coordinated in a square antiprism arrangement, and the Fe（Ⅲ） or Co（Ⅲ） ion in a nearly regular octahedral environment The [LnM（CN）6（DMSO）4（H2O）3]·H2O （Ln = Ce and M = Fe for 1; Ln = La and M = Co for 2） species are held together via hydrogen bonds by coordinated water molecules, lattice water molecules and nitrogen atoms of cyanide groups to form a three-dimensional framework.

HYDROFORMYLATION OF MMA CATALYZED BY SILICA-SUPPORTED POLY-γ-AMINO PROPYLSILOXANE-Rh-Co BIMETALLIC COMPLEX

A silica-supported poly-γ- aminopropylsiloxane-rhodium-cobalt bimetallic complex(abbreviated as SiO_2-NH_2-Rh-Co)has been prepared and used as catalyst for hydroformylationof methyl methacrylate. The results showed that the catalyst could catalyze the reaction in95.6% conversion with 92.8% selectivity for the normal aldehyde, methyl β-formylisobu-tyrate. Such catalyst also showed high stability during the reaction and could be used repeat-edly.

Synthesis and Crystal Structure of a Cyano-bridged Bimetallic Complex[La(betaine)_2(H_2O)_6Fe(CN)_6]·2H_2O

The title complex [La(betaine)2(H2O)6Fe(CN)6]?2H2O (betaine = (CH3)3NCH2CO2) has been synthesized and characterized by X-ray single-crystal structure analysis. The crystal crystallizes in monoclinic, space group P21/n with a = 15.793(5), b = 8.927(3), c = 22.257(7) ?, β = 110.147(5)o, C16H38FeLaN8O12, Mr = 729.31, Z = 4, V = 2946.0(15) ?3, Dc = 1.640 g/m3, μ(MoKα) = 1.988 mm-1, F(000) =1476, R = 0.0388 and wR = 0.0827 for 4237 observed reflections (I > 2σ(I)). The La3+ ion is nine-coordinated by one cyano nitrogen atom and eight oxygen atoms of two betaine and six water molecules. Each complex molecule is connected to form a 3D network structure by some O–H…O and O–H…N hydrogen bonds.

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ln(DMSO)_2(H_2O)(μ-CN)_4Fe(CN)_2] (Ln = Ce and Eu, DMSO = Dimethylsulfoxide) with Layered Structure

Two new bimetallic cyano-bridged complexes [Ln（DMSO）2（H2O）（μ-CN）4Fe（CN）2] （Ln = Ce 1, Eu 2） have been prepared by the grinding reaction method and structurally characterized by X-ray single-crystal structure analysis. Crystallographic data for 1： C10H14CeFeN6O3S2, Mr = 526.36, monoclinic, P2/n, a = 7.852（4）, b = 10.729（5）, c = 11.181（5）A,β = 96.992（8）°, V = 935.0（7） A^3, Z = 2, Dc = 1.870 g/cm^3,/1 = 3.421 mm^-1, F（000） = 512, R = 0.0363 and wR = 0.0971; and those for 2： C10H14EuFeN6O3S2, Mr = 538.20, monoclinic, P21n, a = 7.739（5）, b = 10.668（7）, c = 11.008（7） A,β = 96.943（3）°, V = 902.1（11） A^3, Z = 2, Dc = 1.981 g/cm^3,/1 = 4.499 mm^-1, F（000） = 522, R = 0.0345 and wR = 0.0855. In each complex the lanthanide ion is seven-coordinated in a pentagonal bipyramidal arrangement, and the Fe（Ⅲ） ion is in a nearly regular octahedral environment. The title complexes can be described as two- dimensional （2-D） stair-like structures, which are further connected by hydrogen bonds to form three-dimensional （3-D） frameworks.

Synthesis and Crystal Structure of a Cyano-bridged Bimetallic Complex:[NdFe(CN)_6(DMF)_4(H_2O)_3]H_2O

A new bimetallic cyano-bridged complex, [NdFe(CN)6(DMF)4(H2O)3]H2O (DMF = N,N-dimethylformamide) 1, has been obtained by the reaction of hexacyanoferrate potassium with neodymium (Ⅲ) chloride in H2O/EtOH/DMF (volume ratio: 2:2:1), and its structure was determined by means of single-crystal X-ray diffraction. The compound crystallizes in space group P21/n of monoclinic system with cell parameters: a = 17.646(1), b = 8.9011(3), c = 19.945(1) ? b = 95.835(2)? V = 3116.6(3) ?, Z = 4, Dc = 1.536 g/cm3, Mr = 720.66, F(000) = 1456, m = 2.166 mm-1, R = 0.0386, wR = 0.1120 and S = 1.061. The central Nd (Ⅲ) ion is coordinated by seven oxygen atoms of four DMF molecules and three water molecules and one nitrogen atom of the bridging cyanide in a slightly distorted square-antiprism arrangement, and the Fe (Ⅲ) ion is in an almost octahedral environment coordinated to six cyano-ligands, of which one cyanide ligand bridges the Nd (Ⅲ) ion to form a bimetallic complex. Molecules of complexes in the crystal lattice are held together by hydrogen bonding, forming a three-dimensional framework.

Synthesis and Crystal Structure of a Cyano- bridged Bimetallic Complex[La(DMSO)_3(H_2O)_3- Cr(CN)_6]·H_2O (DMSO = Dimethylsulfoxide) with One-dimensional Chain Molecular Structure

The title complex [La(DMSO)3(H2O)3Cr(CN)6]H2O was obtained by the reaction of LaCl37H2O, DMSO and K3[Cr(CN)6] in aqueous solution on a hot water bath. The crystal crystallizes in orthorhombic, space group P212121 with a = 9.827(3), b = 15.037(4), c = 17.633(5) ? C12H26CrLaN6O7S3, Mr = 653.48, Z = 4, V = 2605.7(13) ?, Dc = 1.666 g/m3, (MoKa) = 2.314 mm-1, F(000) = 1300, R = 0.0205 and wR = 0.0481 for 5038 observed reflec- tions (I > 2s(I)). La3+ ion is eight-coordinated by three DMSO molecules, three H2O molecules and two [Cr(CN)6]3- units. The structure of the title complex possesses a cyano-bridged one- dimensional zigzag chain structure with alternating La(DMSO)3(H2O)3 and Cr(CN)6 moieties, which are linked by some hydrogen bonds to form a 3D network structure.

SPECTROPHOTOMETRIC STUDY OF BIMETALLIC TERNARY COMPLEX OF LANTHANUM——COPPER WITH ALIZARIN FLUORINE BLUE

The bimetallic ternary complex formation in the aqueous solution of La and Cu with alizarin fluorine blue (AFB) was studied by spectrophotometry.The ternary complex LaCu3(AFB)3 has maximum light absorption at 550nm.The colour reaction selectivity is fairly good and the method can be applied to the direct photometric determination of copper in lanthanum or some pure metals.A new mathematical approach to the treatment of spectrophotometric data for differentiation between mononuclear and polynuclear in solution is presented.The improvable fixed logarithm method is for complexes of the type MmBn(m=n) or MmBn(m=n).We report that La(Ⅲ) combines with AFB at pH 4.5 to form a single complex,withm=n=2,La2(AFB)2.

Hetero-bimetallic Complex of a 2D Coordination Network Constructed by Sodium Ion and p-Sulfonatothiacalix[4]arene

A 2D coordination polymer built by sodium ion and water-soluble p-sulfonatothiacalix[4]arene of trivalent yttrium complex [Na（H2O）2Y（H2O）6（DMF） （p-sulfonatothiaca lix[4]arene）]-9H2O is reported. The complex belongs to the monoclinic system, space group P2 1/c, with a = 16.703（3）, b = 17.819（4）, c = 17.357（4）A, β = 106.23（3）°, Z = 4, V = 4960.0（17）A^3, Mr = 1304.08, Dc = 1.746 g/cm^3,μ= 1.624 mm^-1, F（000） = 2688, the final R = 0.0398 and wR = 0.1132 for 7534 observed reflections with I 〉 2σ（I）. One yttrium（Ⅲ） ion is coordinated by the thiacalixarene ligand via the sulfonato group, and also ligated by an oxygen atom of a DMF molecule occupying the cavity of thiacalixarene and six aqua ligands.

Synthesis and Crystal Structure of a Complex Bimetallic Salt [Ni（trans[14]diene）] [Ni （mnt）2]

The title compound has been synthesized by the reaction of [Ni(trans[14]diene)]I2 with Na[Ni(mnt)2] in water and THF, where [trans[14]diene]= 5, 7,7, 12, 14, 14-hexamethyl-1, 4, 8, 11-tetraazacyclotetradeca-4, 11-diene and mnt2- = cis-1, 2-dicyano-1,2-ethylenedithiolato. Its crystal structure has been determined by X-raycrystallography analysis with 4827 independent reflections (Fo】4σ(F0). The bimetallic complex salt [Ni (trans [14] diene )] [Ni (mnt )2] (C24 H32N8Ni2S4, Mr = 678. 24 )crystallizes in the triclinic system with space group P1, a = 9. 2911 (9), b= 11. 7075(12), c=15. 799(2) A, α=68. 384(7), β=79. 324(7), γ=67. 581(6)°, V=1474. 9(3) A3, Dc=1. 527 Mg/m3, Z=2, λ=0. 71073 A, μ=1. 589mm-1, F(000) =704,R=0. 0367. The structure consists of slightly distorted Square planar units [Ni(trans[14]diene)]2+ and [Ni(mnt)2]2-.

Synthesis and Crystal Structure of a Complex Bimetallic Salt [Ni(trans_[14]diene)] [Ni (mnt)_2]

The title compound has been synthesized by the reaction of [Ni(trans[14]diene)]I2 with Na[Ni(mnt)2] in water and THF, where [trans[14]diene]= 5, 7,7, 12, 14, 14-hexamethyl-1, 4, 8, 11-tetraazacyclotetradeca-4, 11-diene and mnt2- = cis-1, 2-dicyano-1,2-ethylenedithiolato. Its crystal structure has been determined by X-raycrystallography analysis with 4827 independent reflections (Fo>4σ(F0). The bimetallic complex salt [Ni (trans [14] diene )] [Ni (mnt )2] (C24 H32N8Ni2S4, Mr = 678. 24 )crystallizes in the triclinic system with space group P1, a = 9. 2911 (9), b= 11. 7075(12), c=15. 799(2) A, α=68. 384(7), β=79. 324(7), γ=67. 581(6)°, V=1474. 9(3) A3, Dc=1. 527 Mg/m3, Z=2, λ=0. 71073 A, μ=1. 589mm-1, F(000) =704,R=0. 0367. The structure consists of slightly distorted Square planar units [Ni(trans[14]diene)]2+ and [Ni(mnt)2]2-.

Polynuclear Lanthanoid Complexes Containing Aluminium—The Structure of[HoAl(CF_3COO)_2(CF_3CHOO)(C_2H_5)_2(C_4H_8O)_2]_2 at 233K

[HoAl(CF_3COO)_2(CF_3CHOO)(C_2H_5)_2(C_4H_8O)_2]_2,Mr=1468.7,monoclinic,P 2_1/n,a=1.0084(4), b=1.8453(6),c=1.4501(6)nm,β=102.40(3)°,V=2.6355(1)nm^3,Z=2,D_c=1.81gcm^(-3),F(000)=1511, T=233K,Mo Kα radiation(λ=0.071069nm).R=0.052 for 6176 unique reflections[Ⅰ≥36(Ⅰ)].The structural units consist of dimeric molecules with the mixed ligand and central bimetallic atoms,which are polynuclear lanthanoid complexes containing aluminium.Ho-Ho'distance is 0.3619(1)nm.The coordination polyhedron of Ho can be described in terms of a distored bicap-prism.

Syntheses and Structural Characterizations of η~5-2,4-Cyclopentadien-1-yl Di-carbonyliron Heteronuclear Bi-Metallic Complexes

The novel complexes, Cp(CO) 2FeTiCp 2Cl(1) and Cp(CO) 2FeSn(CH 2CMe 2Ph) 3(2), were synthesized and characterized by means of elemental analyses and IR spectra, Cp(CO) 2FeSn· (CH 2CMe 2Ph) 3 was additionally characterized by X ray crystal structure analysis. The results of the elemental analyses are in good agreement with the theoretical values. The IR spectra show the existence of η 5 2,4 cyclopentadien 1 yl, carbonyl and methyl groups in the title complexes. The above experimental results show that the M-M bond exists in Cp(CO) 2FeSn· (CH 2Me 2Ph) 3, while the existence of the M-M bond in Cp(CO) 2FeTiCp 2Cl is highly possible, too. Both the two complexes are rather stable towards air and moisture, easily soluble in tetrahydrofuran and toluene, while their solubilities are greatly different in n hexane.

Binuclear Lanthanide Complexes Containing SodiumSyntheses and Crystal Structure of (C_5Me_5)_2Nd(μ-Cl)_2Na(DME)_2 and (C_5Me_5)_2Nd(μ-OCH_3)_2Na(DME)_2

The reaction of NdCl_3 with NaC_5Me_5 generates a novel complex (C_5Me_5)_2Nd(μ-Cl)_2Na(DME)_2 (1). Then (1) reacts with 1 mol ratio Na and a little methyl-naphthalene generating another novel complex (C_5Me_5)_2Nd(μ-OCH_3)_2Na(DME)_2 (2).Complex (1) belongs to orthorhombic crystal system,space group Pbn2_1 with a=1.2635(3) nm,b=1.6127(5) nm,c=1.6543(4J nm,V=3.371(2) nm^3,D_c=1.36 gcm^(-3) and Z=4.The central metal Nd is coordinated by two C_5Me5 ring centroids and two μ-chlorine atoms forming a distorted tetrahedron.The crystal of complex (2) is monoclinic,space group C2/n with a=1.7482(5) nm, b=1.3260(4) nm,c=1.6406(7) nm,β=109.39(3)°,V=3.5874(1) nm^3,D_c=1.26 gcm^(-3) and Z=4,Two five-membered ring centroids and two p-oxygens of OCH_3 form a distorted tetrahedron around the central neodymium ion.

三联苯基配体稳定的锇-锗配合物合成及表征

研究了锇-锗单键双金属配合物[OsGe(ArTrip)(PPh_(3))(H)Cl_(2)](1)的反应性,其中ArTrip=C_(6)H_(3)-2-(η^(6)-Trip)-6-Trip,Trip=2,4,6-iPr_(3)-C_(6)H_(3)。通过与不同试剂反应,成功合成并表征了3个新型锇-锗双金属配合物。通过配合物1与EtMgBr反应合成了锗原子上氯原子被溴原子取代的产物[OsGe(ArTrip)(PPh_(3))(H)Br_(2)](2);1与LiHBEt_(3)反应合成了锗原子上氯原子被乙基取代的产物[OsGe(ArTrip)(PPh_(3))(H)Et_(2)](3);1与HBF4作用合成了加成产物[OsGe(ArTrip)(PPh_(3))(H)_(2)Cl_(2)]BF_(4)(4)。配合物4不稳定,在H_(2)O(nH_(2)O/n_(4)=1)作用下能转化为配合物1。

可用于近紫外LED芯片的铕-铱双金属配合物红光共聚荧光粉

本研究以Ir配合物FIrPic作为Eu离子的配体,合成了一种新的Eu-Ir双金属配合物Eu(FIrPic)_(2)(Phen)UA,并通过自由基聚合成功制备了红色发光荧光共聚物PM-Eu-Ir,适用于商用近紫外芯片型LED。在不影响Eu^(3+)离子的荧光发射特性的前提下,加入Ir-配合物可以有效地敏化Eu^(3+)离子,增强其对400 nm紫外光的吸收。在365 nm紫外光激发下,共聚物PM-Eu-Ir在612 nm处显示出最强的发射峰,其CIE坐标为(0.461,0.254),这与365 nm近紫外芯片非常吻合。红色共聚荧光粉PM-Eu-Ir的微观形貌为典型的多层空间网络结构,除了表现出明显的红光发射和634.54μs的荧光寿命外,还在25~250℃的宽温范围内具有优异的热稳定性。使用共聚物PM-Eu-Ir制作的LED发出的红光亮度为149800 cd/m^(2)。研究结果表明,所制备的共聚荧光粉可作为红光元件用于制造近紫外芯片白光LED。