[M(en)3]2Sn2Se6(M=Mn,Zn)的制备及其热稳定性

用有机溶剂热生长技术(SolvothermalTechnique)制备过渡金属锰和锌硒化物[Mn(en)3]2Sn2Se6(Ⅰ),[Zn(en)3]2Sn2Se6(Ⅱ).用单晶X射线衍射技术对其进行晶体结构分析.[Zn(en)3]2Sn2Se6样品的热分析结果表明,该化合物的热分解分三步进行.光学性质测试表明它们是半导体材料,[Mn(en)3]2Sn2Se6的能带隙为1.76eV.[Zn(en)3]2Sn2Se6的能带隙为2.49eV.     

Novel polyselenidoarsenate and selenidoarsenate: solvothermal synthesis and characterization of [Co(phen)3][As2Se2(μ-Se3)(μ-Se5)] and [Co(phen)3]2[As8Se14

Novel cobalt polyselenidoarsenate [Co(phen)(3)][As(2)Se(2)(μ-Se(3))(μ-Se(5))] (1; phen = 1,10-phenanthroline) was methanolothermally synthesized by the reaction of CoCl(2), As(2)O(3), and Se templated by phen in a CH(3)OH solvent at 130 °C. The same reaction in a H(2)O solvent yielded cobalt selenidoarsenate [Co(phen)(3)](2)[As(8)Se(14)] (2). In 1, the AsSe(+) units are alternately joined by the μ-Se(3)(2-) and μ-Se(5)(2-) bridging ligands to form a novel helical polyselenidoarsenate chain [As(2)Se(2)(μ-Se(3))(μ-Se(5))(2-)](∞). In 2, eight pyramidal AsSe(3) units are connected via corner sharing into the new member of the selenidoarsenate aggregate [As(8)Se(14)](4-) with a condensation grade of 0.571, which represents the first discrete selenidoarsenate(III) with a condensation grade of above 0.50. The octahedral complex [Co(phen)(3)](2+) is formed in situ to act as a countercation in compounds 1 and 2. 1 and 2 exhibit steep absorption band gaps at 2.09 and 2.16 eV, respectively.     

Synthesis,structure, and electrochemical properties of [M(N-MeIm)6]2+ (M = Ni,Co, Cu) associated with [HgCl4]2−

Reaction of Hg(NO₃)₂ with 4 equivalent KI in water afford K₂[HgI₄]. By using K₂[HgI₄] as the precursor, three new heterobimetallic compounds [Ni(N-MeIm)₆][HgI₄] (I), [Co(N-MeIm)₆][HgI₄] (II), and [Cu(N-MeIm)₆][HgI₄] (III) have been characterized by elemental analysis, IR spectra, and the singlecrystal X-ray crystallorgraphy analysis. Three complexes are isomorphous and crystallized in monoclinic symmetry space group P2₁/c. The coordination around each center metal(II) atom is octahedral with six nitrogen atoms of N-MeIm ligand. Each structure contains one tetrahedral [HgI₄]^2? as an anion to balance the charge of the molecular. Thermogravimetry analysis indicates these complexes have the similar departure process and cyclic voltammogram exhibits a significant pair of redox peaks.     

As-5、[As5M]-、[As5MAs5]2- (M=Ti,Zr, Hf)的结构和芳香性

用密度泛函理论(DFT)研究了As-5、[As5M]-和[As5MAs5]2- (M=Ti, Zr, Hf)的结构、频率、能量以及芳香性, 详细讨论了体系中不同类型的键和电子如化学键、孤对电子、核电子等对总的核独立化学位移(NICS)的影响. 结果表明, As-5、[As5M]-和[As5MAs5]2-的基态结构分别具有D5h、C5v和D5h对称性, 而且都具有芳香性. As-5 (D5h)的芳香性主要来源于As—As π键和As—As σ键的作用. [As5M]-(C5v)中各种As—M键的NICS分割值占主要优势, 其次是As—As之间形成的σ键. [As5TiAs5]2-(D5h)中, As—As π键的作用占主要优势. [As5ZrAs5]2-(D5h)中, As—As π键对体系总的NICS贡献相对减小, 而As—Zr键的作用增强. [As5HfAs5]2-(D5h)的芳香性主要来自As—Hf键的作用.     

Double sandwich polyoxometalate and its Fe(III) substituted derivative, [As2Fe5Mo21O82]17– and [As2Fe6Mo20O80(H2O)2]16–

A double sandwich polyoxometalate and its Fe(III) substituted derivative, [As(2)Fe(5)Mo(21)O(82)](17-) (1) and [As(2)Fe(6)Mo(20)O(80)(H(2)O)(2)](16-) (2), were synthesized and characterized by single-crystal X-ray diffraction, infrared spectroscopy, fluorescent spectroscopy, UV spectra, thermogravimetry-differential scanning calorimetry analyses, electrospray ionization mass spectrometry, and magnetism measurements. The polyoxoanion is composed of a central fragment FeMo(7)O(28) for 1 (Fe(2)Mo(6)O(26)(H(2)O)(2) for 2) and two external AsMo(7)O(27) fragments linked together by two distinct edge-sharing dimeric clusters Fe(2)O(10) to lead to a C(2v) molecular symmetry. The central FeMo(7)O(28) fragment and external AsMo(7)O(27) fragment have a similar structure, and both of them can be viewed as a monocapped hexavacant α-Keggin subunit with a central FeO(4) group or a central AsO(3) group. Both of the polyoxoanions contain a oxo-bridged Fe(III)(5) magnetic core with the angles of Fe-O-Fe in the range of 96.4(4)-125.7(5)°, and magnetism measurements show an overall ferromagnetic interactions among the five-nuclearity cluster Fe(5) with the spin ground state S = 15/2.     

Synthesis and characterization of one-dimensional coordination polymers, [M(sac)2(μ–pyz)(H2O)2] n [M=ZnII,CdII, pyz = pyrazine,and sac = saccharinate]

Two new coordination polymers, [M(sac)₂(μ–pyz)(H₂O)₂] _n [M=Zn^II(1), Cd^II(2), pyz =?pyrazine, and sac =?saccharinate], have been prepared and characterized by elemental analysis, FTIR spectroscopy, thermal analysis and single crystal X-ray diffraction. Both complexes are isomorphous and crystallize in the triclinic P 1 space group. The metal(II) ions are octahedrally coordinated by two sac, two aqua and two pyz ligands. The sac ligands are N-coordinated, while the pyz ligands are bridges between the metal centers, leading to one-dimensional linear chains. Intra-chain M–M separations in 1 and 2 are 7.218 and 7.498 Å, respectively. The individual chains are linked by strong OW–H ··· O(sac) hydrogen bonds into two–dimensional layers, which are further assembled into three–dimensional supramolecular networks by aromatic π(sac) ··· π(sac) stackings interactions.     

Synthesis, properties, and thermal decomposition of compounds [Co(En)3][Fe(CN)6] · 2H2O and [Co(En)3]4[Fe(CN)6]3 · 15H2O

Binary complex salts, [Co(En)₃][Fe(CN)6] · 2H₂O and [Co(En)₃]₄[Fe(CN)₆]₃ · 15H₂O, are synthesized. The properties of the salts and their thermolysis in air, dihydrogen, and argon are studied. Oxides of the central ions of the binary complex salts are found to be the thermolysis products in an oxidative atmosphere. Solid solutions (intermetallic compounds) CoFe are the thermolysis products in the reductive atmosphere, whereas intermetallides containing considerable amounts of C and N and an impurity of Co and Fe oxides are the thermolysis products in an inert atmosphere. Gaseous thermolysis products in dihydrogen and argon are NH₃, hydrocarbons, and ethylenediamine.     

Formation of M(4)Se(4) cuboids (M = As, Sb, Bi) via secondary pnictogen-chalcogen interactions in the co-crystals MX(3)·Se[double bond, length as m-dash]P(p-FC(6)H(4))(3) (M = As, X = Br; M = Sb, X = Cl; M = Bi, X = Cl, Br)

The reactions of the group 15 trihalides, MX(3) (M = As, Sb, Bi; X = Cl, Br), with the phosphine selenide SeP(p-FC(6)H(4))(3) result in the formation of co-crystals of formula MX(3)·SeP(p-FC(6)H(4))(3). No reaction was observed with MI(3) (M = As, Sb, Bi). The structures of MX(3)·SeP(p-FC(6)H(4))(3) (M = As, X = Br 2; M = Sb, X = Cl 3; M = Bi, X = Cl 5; M = Bi, X = Br 6) have been established, and are isomorphous, crystallising in the cubic I23 space group. All the structures feature a primary MX(3) unit, which has three weak secondary MSe interactions to SeP(p-FC(6)H(4))(3) molecules. However, each of these SeP(p-FC(6)H(4))(3) molecules bridges three MX(3) molecules, resulting in the generation of an M(4)Se(4) (M = As, Sb, Bi) distorted cuboid linked by the pnictogen-chalcogen interactions. Four opposing corners of the cuboid are occupied by the M atom (M = As, Sb, Bi) of an MX(3) pyramid, and the other four by the selenium atom of the phosphine selenide.     

Synthesis, structures, and properties of molybdenum and tungsten chalcogenide cubane complexes (NH4)6[M4Q4(CN)12]·6H2O (M=Mo or W; Q=S or Se)

Four new chalcogenide molybdenum and tungsten cubane clusters (NH₄)₆[M₄Q₄(CN)₁₂]·6H₂O (M=Mo or W; Q=S or Se) were prepared by high-temperature reactions of the triangular M₃O₇Br₄ complexes with KCN at 430 °C followed by crystallization from aqueous solutions of ammonium acetate. The molecular and crystal structures of (NH₄)₆[Mo₄S₄(CN)₁₂]·6H₂O, (NH₄)₆[W₄S₄(CN)₁₂]·6H₂O, and (NH₄)₆[W₄Se₄(CN)₁₂]·6H₂O were established by X-ray diffraction analysis. The mixed-valence cubane clusters are diamagnetic and isostructural and have the symmetryT _d . The clusters were characterized by IR and electronic spectroscopy. The data of cyclic voltammetry demonstrated that the [M₄Q₄(CN)₁₂] ⁿ⁻ clusters exist in three oxidation states from the most oxidized (n=6; 10 cluster electrons) to the most reduced electron-precise 12-electron species (n=8). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 18–24, January, 2000.     

[M(dap)3]2(Sb2Se5)·xH2O(M=Ni,x=2;M=Zn,x=0)的溶剂热合成及晶体结构

利用溶剂热法合成了2种新的有机杂化锑硒化合物[Ni(dap)3]2(Sb2Se5)].2H2O(1)和[Zn(dap)3]2(Sb2Se5)](2)(dap=1,2-丙二胺),单晶X射线衍射分析结果表明,1属于三方晶系,P3121空间群,晶胞参数为a=10.7574(14),b=10.7574(14),c=31.672(4),γ=120.00°,z=4。2属于单斜晶系,P21空间群,晶胞参数为a=10.772(2),b=16.391(3),c=11.704(2),β=100.912(4)°,z=4。在2种化合物中,Ni2 与Zn2 离子分别与3个dap配体螯合形成畸变八面体几何构型,其中dap配体的N原子是无序的,而二聚[Sb2Se5]2-阴离子是由2个SbSe3三角锥共用1个Se原子连接而成。     

Sr(Ag1−xLix)2Se2 and [Sr3Se2][(Ag1−xLix)2Se2] Tunable Direct Band Gap Semiconductors

Synthesizing solids in molten fluxes enables the rapid diffusion of soluble species at temperatures lower than in solid-state reactions, leading to crystal formation of kinetically stable compounds. In this study, we demonstrate the effectiveness of mixed hydroxide and halide fluxes in synthesizing complex Sr/Ag/Se in mixed LiOH/LiCl. We have accessed a series of two-dimensional Sr(Ag_1−xLi_x)₂Se₂ layered phases. With increased LiOH/LiCl ratio or reaction temperature, Li partially substituted Ag to form solid solutions of Sr(Ag_1−xLi_x)₂Se₂ with x up to 0.45. In addition, a new type of intergrowth compound [Sr₃Se₂][(Ag_1−xLi_x)₂Se₂] was synthesized upon further reaction of Sr(Ag_1−xLi_x)₂Se₂ with SrSe. Both Sr(Ag_1−xLi_x)₂Se₂ and [Sr₃Se₂][(Ag_1−xLi_x)₂Se₂] exhibit a direct band gap, which increases with increasing Li substitution (x). Therefore, the band gap of Sr(Ag_1−xLi_x)₂Se₂ can be precisely tuned via fine-tuning x that is controlled by only the flux ratio and temperature.     

Assembly of One to Four As4 Analogues, (Ge2As2)2− or (Ge3As)3−, in the Coordination Sphere of [PhM]+, [MesM]+, or M2+ (M=Zn,Cd, Hg)

Pseudo-tetrahedral units of p-block atoms proved to be excellent building blocks for novel molecular architectures and for introducing new elemental combinations which are not otherwise accessible. In this work, we present a series of clusters obtained by reactions of binary Ge/As anions with [MPh₂] (M=Zn, Cd, Hg; Ph=phenyl). The study is grounded on the fact that the binary reactant gained by extracting the solid ‘K₂GeAs’ with ethane-1,2-diamine (en) co-exists as (Ge₂As₂)²⁻ and (Ge₃As)³⁻ in solution. This allows for a larger variety of products by ‘selecting’ the most suitable species for the final ternary complex to crystallize. The reactions afforded the unprecedented first step of the corresponding interaction, thus attachment of (MPh)⁺ to a pseudo-tetrahedral unit in [PhZn(Ge₃As)]²⁻ ( 1 ) and [PhHg(Ge₃As)]²⁻ ( 2 ), and complex anions with two, three, or four units, [(Ge₃As)Zn(Ge₂As₂)]³⁻ ( 3 ), [Cd₃(Ge₃As)₃]³⁻ ( 4 ), and [Zn₃(Ge₃As)₄]⁶⁻ ( 5 ). Quantum chemistry confirmed the compositions and the positions of the Ge or As atoms, beside explaining structural peculiarities. The subtle impact of different [MR₂] reactants was additionally studied by corresponding reactions using [ZnMes₂] (Mes=mesityl), which showed success in selectively crystallizing [MesZn(Ge₃As)]²⁻ ( 6 ). Based on our findings, we derive a suggestion of the underlying reaction cascade.     

Self-assembly, crystal structures, and properties of metal-2-sulfoterephthalate frameworks based on [M4(μ3-OH)2]6+ clusters (M = Co, Mn, Zn and Cd)

Hydro- and solvo-thermal reactions of d-block metal ions (Mn(2+), Co(2+), Zn(2+) and Cd(2+)) with monosodium 2-sulfoterephthalate (NaH(2)stp) form six 3D coordination polymers featuring cluster core [M(4)(μ(3)-OH)(2)](6+) in common: [M(2)(μ(3)-OH)(stp)(H(2)O)] (M = Co (1), Mn (2) and Zn (3)), [Zn(2)(μ(3)-OH)(stp)(H(2)O)(2)] (4), [Zn(4)(μ(3)-OH)(2)(stp)(2)(bpy)(2)(H(2)O)]·3.5H(2)O (5) and [Cd(2)(μ(3)-OH)(stp) (bpp)(2)]·H(2)O (6) (stp = 2-sulfoterephthalate, bpy = 4,4'-bipyridine and bpp = 1,3-di(4-pyridyl)propane). All these coordination polymers were characterized by single crystal X-ray diffraction, IR spectroscopy, thermogravimetric and elemental analysis. Complexes 1-3 are isostructural coordination polymers with 3D frameworks based on the chair-like [Zn(4)(μ(3)-OH)(2)](6+) core and the quintuple helixes. In complex 4, there exist double helixes in the 3D framework based on the chair-like cluster cores. Complex 5 possesses a 2-fold interpenetration structure constructed from boat-like cluster core and the bridging ligands stp and bpy. For complex 6, the chair-like cluster cores and stp ligands form a 2D (4,4) network which is further pillared by bpp linkers to a 3D architecture. Magnetic studies indicate that complex 1 exhibits magnetic ordering below 4.9 K with spin canting, and complex 2 shows weak antiferromagnetic coupling between the Mn(II) ions with g = 2.02, J(wb) = -2.88 cm(-1), J(bb) = -0.37 cm(-1). The fluorescence studies show that the emissions of complexes 3-6 are attributed to the ligand π-π* transition.     

Synthesis and structural characterisation of new ettringite and thaumasite type phases: Ca6[Ga(OH)6·12H2O]2(SO4)3·2H2O and Ca6[M(OH)6·12H2O]2(SO4)2(CO3)2, M = Mn,Sn

Investigations into the formation of new ettringite-type phases with a range of trivalent and tetravalent cations were carried out to further study the potential this structure type has to incorporate cations covering a range of ionic radii (0.53–0.69 Å). We report the synthesis and structural characterisation of a new ettringite-type phase, Ca₆[Ga(OH)₆·12H₂O]₂(SO₄)₃·2H₂O, which was indexed in space group P31c with the unit cell parameters a = 11.202(2) Å, c = 21.797(3) Å and two new thaumasite-type phases Ca₆[M(OH)₆·12H₂O]₂(SO₄)₂(CO₃)₂, M = Mn, Sn which were indexed in space group P6₃ with the unit cell parameters a = 11.071(5) Å, c = 21.156(8) Å and a = 11.066(1) Å, c = 22.420(1) Å respectively. These new phases show the versatility of the ettringite family of structures to tolerate a large range of cation sizes on the octahedral M site and highlights the preference of tetravalent cations to crystallise with the thaumasite structure over the ettringite structure.     

First example of the cluster ammine complex [Re6Se7Br(NH3)6]3+: synthesis and structure of the [Re6Se7Br(NH3)6][Re6Se7BrBr6]·12H2O salt

The reaction of Cs₃[Re₆Se₇BrBr₆] with aqueous ammonia afforded the octahedral rhenium ammine cluster complex cation [Re₆Se₇Br(NH₃)₆]³⁺. This cation crystallized as the [Re₆Se₇Br(NH₃)₆][Re₆Se₇BrBr₆]·12H₂O compound. The crystal structure of this compound was established. The presence of the NH₃ ligands in the coordination environment about the Re atom was confirmed by thermogravimetry, vibrational spectroscopy, and high-resolution mass spectrometry. The resulting compound is the first example of salts composed of the cluster cation and cluster anion possessing the same {Re₆Se₇Br} cluster core.     

Hydrothermal Synthesis and Characterization of Two New Phosphatomolybdates(V) Containing Sandwich-Shaped [M(Mo6P4)2] Clusters (M = Co, Ni)

A new hybrid material, (H₂dien)₂(Hamimi)₂[Co₃Mo₁₂O₂₄(OH)₆(HPO₄)₆(PO₄)₂]₂ · nH₂O (1) (n = 5.26), was hydrothermally synthesized via a simultaneous in situ cyclization of acetic acid and diethylenetriamine to 1-(2-aminoethyl)-2-methyl-2-imidazoline. The sandwich-shaped [Co(Mo₆P₄)₂] clusters in 1 are linked by tetrahedrally coordinated cobalt into two-dimensional layers. It is interesting that no 2-imidazoline group was observed when the starting Co(II) salt was replaced by Ni(II) salt under the same hydrothermal conditions, but it led to the isolation of (Hdien)₂[NiMo₁₂O₂₄(OH)₆(H₂PO₄)₆(HPO₄)₂] · 2dien · 8H₂O (2), in which the [Ni(Mo₆P₄)₂] units are discrete. A probe reaction of the oxidation of acetaldehyde with H₂O₂ showed that both compounds have high catalytic activity in the reaction. Compound 1 crystallizes in the space group C2/c with a = 26.028(4), b = 12.3391(17), c = 25.555(4) Å, β = 98.876(12)°, V = 8109(2) Å³ and Z = 4. Compound 2 is in the space group P2₁/n with a = 13.206(3), b = 22.170(5), c = 13.627(3) Å, β = 103.437(5)°, V = 3880.7(15) ų and Z = 2.     

Synthesis and structures of zirconium complexes [Et2H2N]+2[ZrCl6]2–, [Me3NCH2Ph]+2[ZrCl6]2–•MeCN, [Ph3PC6H4(CHPh2-4)]+2[ZrCl6]2–•2 MeCN,and [Ph4Sb]+2[ZrCl6]2–

Russian Chemical Bulletin - The complexes [Et2H2N]+2[ZrCl6]2– (1), [Me3NCH2Ph]+2[ZrCl6]2–?MeCN (2), [Ph3PC6H4(CHPh2-4)]+2[ZrCl6]2–?2 MeCN (3), and...