以PW9为结构基元构筑的夹心型多金属氧酸盐化合物的合成与晶体结构

通过水热合成方法合成了以夹心多酸阴离子{Ni₄(H₂O)₂(PW₉O₃₄)₂}^10-,乙二胺(en)和Ni(Ⅱ)构筑的夹心型多金属氧酸盐化合物[Ni(en)₂]₂[{Ni(en)₂}{Ni(en)₂H₂O}₂{(PW₉O₃₄)₂Ni₄(H₂O)₂}]·16H₂O(1),采用IR、单晶X-射线衍射法、TG/DTG及循环伏安法对标题化合物进行结构和性质研究。该化合物的夹心多酸阴离子通过[Ni(en)₂]²⁺连接形成一维链,并进一步通过氢键作用形成3D超分子结构。     

阳离子(从有机铵到无机阳离子)对fac-[Fe(CO)3I3]-阴离子的稳定性和毒性的调节

通过无机碘盐(MI_n)与cis-[Fe (CO)₄I₂]反应制备了5个盐类化合物fac-M[Fe (CO)₃I₃]_n(Mⁿ⁺=Na⁺(1),K⁺(2),Mg²⁺(3),Ca²⁺(4),NH⁴⁺(5)),探讨了阳离子Mⁿ⁺对fac-[Fe (CO)₃I₃]^-阴离子的稳定性和细胞毒性的影响。通过傅里叶变换红外光谱(FTIR)监测,发现盐1~5在DMSO、D₂O、生理盐水等介质中均能缓释CO,其释放动力学符合一级反应动力学模型;还发现溶液中碘离子的浓度和酸度对该阴离子的缓释CO性能也具有调节作用。通过噻唑蓝(MTT)实验评估了盐1~5对膀胱癌细胞的毒性,其24 h半抑制浓度(IC₅₀)在25~43 μmol·L^-1。与有机铵阳离子类的盐化合物相比,盐1~5在含水介质中的释放CO速率下降,毒性亦有下调。研究还发现这类fac-[Fe (CO)₃I₃]^-阴离子在缓释CO的同时释放碘自由基,并能导致线粒体活性氧(ROS)水平、Parkin蛋白表达均上调。铁死亡抑制剂(Ferrostatin-1和Liproxstatin-1)试验结果表明这类化合物可能引发铁死亡通路并促进肿瘤细胞死亡。     

以PW9为结构基元构筑的夹心型多金属氧酸盐化合物的合成与晶体结构

通过水热合成方法合成了以夹心多酸阴离子{Ni₄(H₂O)₂(PW₉O₃₄)₂}^10-,乙二胺(en)和Ni(Ⅱ)构筑的夹心型多金属氧酸盐化合物[Ni(en)₂]₂[{Ni(en)₂}{Ni(en)₂H₂O}₂{(PW₉O₃₄)₂Ni₄(H₂O)₂}]·16H₂O(1),采用IR、单晶X-射线衍射法、TG/DTG及循环伏安法对标题化合物进行结构和性质研究。该化合物的夹心多酸阴离子通过[Ni(en)₂]²⁺连接形成一维链,并进一步通过氢键作用形成3D超分子结构。     

无机-有机杂化硫属化合物[Mn（1，2-dap）2（H2O）]2（μ-Sn2Q6）（Q=S、Se）和[Mn（tren）]2（μ-Sn2S6）的合成、晶体结构与性能

采用溶剂热方法合成了3个多元硫属化合物[Mn（1,2-dap）₂（H₂O）]₂（μ-Sn₂Q₆）（Q=S（1）和Se（2））和[Mn（tren）]₂（μ-Sn₂S₆）（3）,用X-射线单晶衍射测定了化合物的结构,并通过红外光谱、紫外-可见漫反射光谱对其进行了表征。单晶结构解析表明,化合物1和2都属于正交晶系,Pccn空间群（No.56）,晶体结构是由[Mn（1,2-dap）₂（H₂O）]²⁺配合物阳离子和[Sn₂Q₆]^4-二聚体通过Mn-Q键连接而成的[Mn（1,2-dap）₂（H₂O）]₂（μ-Sn₂Q₆）低聚体,相邻的低聚体之间通过氢键相连形成三维结构。化合物3属于三斜晶系,晶体结构是由[Mn（tren）]₂（μ-Sn₂S₆）单元通过氢键连接而成的二维结构。紫外-可见漫反射光谱结果显示化合物1,2和3的带隙分别为2.5,2.1,2.4eV,属于半导体材料。     

一个基于β-[Mo8O26]和5-（3-吡啶基）-四唑桥连的二核镍配合物构筑的无机-有机杂化化合物

通过水热合成了一种有机-无机杂化化合物[Ni₄（3-Hpt）₆（H₂O）₁₀Mo₈O₂₆]·Mo₈O₂₆·10H₂O（3-Hpt=5-（3-吡啶基）-四唑）,IR和X-射线单晶衍射实验测定和结构解析结果表明,该化合物是由双支撑形结构的[Ni₄（3-Hpt）₆（H₂O）₁₀Mo₈O₂₆]阳离子,β构型[Mo₈O₂₆]簇阴离子及晶格水组成的。在阳离子中,β构型[Mo₈O₂₆]簇通过中心对称的2个端基氧与2个双核配阳离子[Ni₂（3-Hpt）₃（H₂O）₅]⁴⁺的镍原子配位形成双支撑形结构。将所得化合物制成碳糊电极（1-CPE）,该电极在酸性水溶液中对亚硝酸根,溴酸根的还原有较好的催化活性。     

N-(1-亚氨基乙基)乙脒铂配合物合成、结构和性质

四氯合铂酸钾分别与邻、间、对磺基苯甲酸在乙腈和水中利用水热合成获得了3个铂的N-(1-亚氨基乙基)乙脒配合物:[Pt(NIA)₂]·(2-sb)·2H₂O(1),[Pt(NIA)₂]·(3-sb)·3H₂O(2)和[Pt(NIA)₂]·(1,4-dsb)·2H₂O(3)(NIA=N-(1-亚氨基乙基)乙脒,2-sb^2-=2-磺基苯甲酸二价阴离子、3-sb^2-=3-磺基苯甲酸二价阴离子、1,4-dsb^2-=1,4-二磺基苯二价阴离子)。合成过程中发生了乙氰三聚以及4-sb^2-转变为1,4-dsb^2-的反应。对配合物进行了元素分析、红外、紫外、荧光、热重和粉末X射线衍射表征,并利用单晶X射线衍射测定了配合物的晶体结构。3个配合物为阳离子-阴离子物种,阳离子为[Pt(NIA)₂]²⁺,中心金属离子四配位平面构型;阴离子与阳离子、水形成氢键,组成一个三维网络结构,但3个配合物的氢键模式不同。配合物在热稳定性、荧光性质上有一定差异。     

手性化合物[Co（L/D-thr）3]·4.5H2O的合成、结构以及圆二色性

合成了2个基于手性配体L-和D-苏氨酸（L/D-thr）的Co（Ⅲ）配合物的对应异构体[Co（L-thr）3]·4.5H₂O（L-1）和[Co（L-thr）₃]·4.5H₂O（D-1）,并对2个化合物进行了单晶X射线衍射、红外、热重、紫外可见光谱以及CD谱性质研究。晶体结构分析表明,2个化合物分别结晶在四方晶系P4₃2₁2和P4₁2₁2手性空间群。固体CD谱测试进一步证实2个化合物具有手性。     

手性化合物[Co(L/D-thr)3]·4.5H2O的合成、结构以及圆二色性

合成了2个基于手性配体L-和D-苏氨酸（L/D-thr）的Co（III）配合物的对应异构体[Co（L-thr）₃]·4.5H₂O（L-1）和[Co（L-thr）₃]·4.5H₂O（D-1）,并对2个化合物进行了单晶X射线衍射、红外、热重、紫外可见光谱以及CD谱性质研究。晶体结构分析表明,2个化合物分别结晶在四方晶系P4₃2₁2和P4₁2₁2手性空间群。固体CD谱测试进一步证实2个化合物具有手性。     

对称性破缺：手性高氯酸乙酸·二(乙二胺)合锌(Ⅱ)的合成与结构

用简单的非手性原料醋酸锌和乙二胺在高氯酸钠的甲醇溶液中反应,反应过程中发生了对称性破缺现象,得到了一对对映体Δ-cis-[Zn（en）₂Ac][ClO₄]（Δ-1）and Λ-cis-[Zn（en）₂Ac][ClO₄]（Λ-1）（en=乙二胺,Ac-=醋酸根）。用元素分析、红外光谱、CD光谱和X-ray单晶衍射对产物进行了表征。X-ray单晶衍射结果表明配合物Δ-cis和Λ-cis中的锌（Ⅱ）离子均与2个乙二胺上的4个氮原子和醋酸根上的2个氧原子顺式配位,形成六配位畸变的八面体构型。{Δ-cis-[Zn（en）₂Ac]}⁺和{Λ-cis-[Zn（en）₂Ac]}⁺单体通过氢键作用分别形成具有右手和左手双螺旋的一维链。用X-ray单晶衍射和CD光谱确定了配合物的手性特征。     

基于双核{Zn2(COO)4}次级构筑单元的二维发光配位聚合物的晶体结构和对Fe3+的检测

使用H2L配体（H2L=2-（1,3-dioxo-1H-benzo[de]isoquinolin-2（3H）-yl） terephthalic acid）和Zn²⁺通过水热反应,合成了一例基于双核{Zn₂（COO）₄}次级构筑单元的二维发光配位聚合物[Zn₂（L）₂（DMSO）₂（DMF）]（1）（DMSO=二甲亚砜,DMF=N,N-二甲基甲酰胺）。拓扑分析表明1结构中的双核{Zn₂（COO）₄}单元可视为4连接节点,并与作为连接子的L^2-形成（4,4）-网拓扑构型。1表现出对Fe³⁺离子的选择性发光猝灭响应,检测限为2.8 μmol·L^-1。1对Fe³⁺的检测具有良好的抗干扰性,且可通过DMF溶剂洗涤实现再生,可多次循环使用。     

有机杂化硫代碲酸盐化合物(H_2en)TeS_3和[Ni(en)_3]TeS_3的溶剂热合成与表征

用低温溶剂热法合成了2种分立结构的有机杂化硫代碲(Ⅳ)酸盐化合物(H2en)TeS3(1)和[Ni(en)3]TeS3(2)(en=乙二胺),通过X-射线单晶衍射,红外光谱,元素分析等手段对它们的结构进行了表征。晶体结构解析结果表明:2个化合物均属单斜晶系,空间群分别为P21和P21/c。化合物1和2具有孤立三角锥[TeS3]2-阴离子,化合物1的平衡阳离子为双质子化乙二胺[H2en]2+,阴离子基团[TeS3]2-和阳离子基团[H2en]2+之间通过N-H…S氢键连接。化合物2的阳离子基团为过渡金属Ni与乙二胺的配合物[Ni(en)3]2+。另外,对该2种晶体进行了紫外-可见漫反射光谱测试和热重分析。     

Structure of two new borates YCa3(AlO)3(BO3)4 and YCa3(GaO)3(BO3)4

By replacing Mn in YCa₃(MnO)₃(BO₃)₄ with trivalent Al and Ga, two new borates with the compositions of YCa₃(MO)₃(BO₃)₄ (M=Al, Ga) were prepared by solid-state reaction. Structure refinements from X-ray powder diffraction data revealed that both of them are isostructural to gaudefroyite with a hexagonal space group P6₃/m. Cell parameters of a=10.38775(13)Å, c=5.69198(10)Å for the Al-containing compound and a=10.5167(3)Å, c=5.8146(2)Å for the Ga analog were obtained from the refinements. The structure is constituted of AlO₆ or GaO₆ octahedral chains interconnected by BO₃ groups in the ab plane to form a Kagomé-type lattice, leaving trigonal and apatite-like tunnels. It is found that most rare-earth and Cr, Mn ions can be substituted into the Y³⁺ and M³⁺ sites, respectively, and the preference of rare-earth ions to locate in the trigonal tunnel is correlated to the sizes of the M³⁺ ions.     

Synthesis and characterisation of HRuRh3(CO)12. Crystal structures of HRuRh3(CO)12, HRuRh3(CO)10(PPh3)2 and HRuCo3(CO)10(PPh3)2

A new ruthenium-rhodium mixed-metal cluster HRuRh₃(CO)₁₂ and its derivatives HRuRh₃(CO)₁₀(PPh₃)₂ and HRuCo₃(CO)₁₀(PPh₃)₂ have been synthesized and characterized. The following crystal and molecular structures are reported: HRuRh₃(CO)₁₂: monoclinic, space group P2₁/c, a 9.230(4), b 11.790(5), c 17.124(9) Å, β 91.29(4)°, Z = 4; HRuRh₃(CO)₁₀(PPh₃)₂·C₆H₁₄: triclinic, space group P$\text{1}$, a 11.777(2), b 14.079(2), c 17.010(2) Å, α 86.99(1), β 76.91(1), γ 72.49(1)°, Z = 2; HRuCo₃(CO)₁₀(PPh₃)₂·CH₂Cl₂: triclinic, space group P$\text{1}$, a 11.577(7), b 13.729(7), c 16.777(10) Å, α 81.39(4), β 77.84(5), γ 65.56°, Z = 2. The reaction between Rh(CO)₄^? and (Ru(CO)₃Cl₂)₂ tetrahydrofuran followed by acid treatment yields HRuRh₃(CO)₁₂ in high yield. Its structural analysis was complicated by a 80–20% packing disorder. More detailed structural data were obtained from the fully ordered structure of HRuRh₃(CO)₁₀(PPh₃)₂, which is closely related to HRuCo₃(CO)₁₀(PPh₃)₂ and HFeCo₃(CO)₁₀(PPh₃)₂. The phosphines are axially coordinated.     

Vaporization of DyI3(s) and thermochemistry of the homocomplexes (DyI3)2(g) and (DyI3)3(g)

The vaporization of DyI₃(s) was investigated in the temperature range between 833 and 1053 K by the use of Knudsen effusion mass spectrometry. The ions DyI₂⁺, DyI₃⁺, Dy₂I₄⁺, Dy₂I₅⁺, Dy₃I₇⁺, and Dy₃I₈⁺ were detected in the mass spectrum of the equilibrium vapor. The gaseous species DyI₃, (DyI₃)₂, and (DyI₃)₃ were identified and their partial pressures determined. Enthalpies and entropies of sublimation resulted according to the second- and third-law methods. The following sublimation enthalpies at 298 K were determined for the gaseous species given in brackets: 274.8±8.2 kJ mol⁻¹ [DyI₃], 356.0±11.3 kJ mol⁻¹ [(DyI₃)₂], and 436.6±14.6 kJ mol⁻¹ [(DyI₃)₃]. The enthalpy changes of the dissociation reactions (DyI₃)₂=2 DyI₃ and (DyI₃)₃=3 DyI₃ were obtained as Δ_dH°(298)=193.3±5.6 and 390.3±13.0 kJ mol⁻¹, respectively.     

Syntheses, structures, and properties of Ag4(Mo2O5)(SeO4)2(SeO3) and Ag2(MoO3)3SeO3

Ag₄(Mo₂O₅)(SeO₄)₂(SeO₃) has been synthesized by reacting AgNO₃, MoO₃, and selenic acid under mild hydrothermal conditions. The structure of this compound consists of cis-MoO₂²⁺ molybdenyl units that are bridged to neighboring molybdenyl moieties by selenate anions and by a bridging oxo anion. These dimeric units are joined by selenite anions to yield zigzag one-dimensional chains that extended down the c-axis. Individual chains are polar with the C₂ distortion of the Mo(VI) octahedra aligning on one side of each chain. However, the overall structure is centrosymmetric because neighboring chains have opposite alignment of the C₂ distortion. Upon heating Ag₄(Mo₂O₅)(SeO₄)₂(SeO₃) looses SeO₂ in two distinct steps to yield Ag₂MoO₄. Crystallographic data: (193 K; MoKα, λ=0.71073 Å): orthorhombic, space group Pbcm, a=5.6557(3), b=15.8904(7), c=15.7938(7) Å, V=1419.41(12), Z=4, R(F)=2.72% for 121 parameters with 1829 reflections with I>2σ(I). Ag₂(MoO₃)₃SeO₃ was synthesized by reacting AgNO₃ with MoO₃, SeO₂, and HF under hydrothermal conditions. The structure of Ag₂(MoO₃)₃SeO₃ consists of three crystallographically unique Mo(VI) centers that are in 2+2+2 coordination environments with two long, two intermediate, and two short bonds. These MoO₆ units are connected to form a molybdenyl ribbon that extends along the c-axis. These ribbons are further connected together through tridentate selenite anions to form two-dimensional layers in the [bc] plane. Crystallographic data: (193 K; MoKα, λ=0.71073 Å): monoclinic, space group P2₁/n, a=7.7034(5), b=11.1485(8), c=12.7500(9) Å, β=105.018(1) V=1002.7(2), Z=4, R(F)=3.45% for 164 parameters with 2454 reflections with I>2σ(I). Ag₂(MoO₃)₃SeO₃ decomposes to Ag₂Mo₃O₁₀ on heating above 550 °C.     

Hydrothermal Syntheses, Structures, and Properties of Two New Potassium Vanadium Phosphates: K3(VO) (V2O3) (PO4)2(HPO4) and K3 (VO) (HV2O3) (PO4)2(HPO4)

Two new potassium vanadium phosphates have been prepared and their structures have been determined from analysis of single crystal X-ray data. The two compounds, K₃(VO)(V₂O₃) (PO₄)₂(HPO₄) and K₃(VO)(HV₂O₃)(PO₄)₂(HPO₄), are isostructural, except for the incorporation of an extra hydrogen atom into the nearly identical frameworks. The structures consist of a three-dimensional network of [VO]_n chains connected through phosphate groups to a [V₂O₃] moiety. Magnetic susceptibility experiments indicate that in the case of the di-hydrogen compound, there are no significant magnetic interactions between the three independent vanadium (IV) centers. Crystal data: for K₃(VO)(V₂O₃)(PO₄)₂ (HPO₄), M_r = 620.02, orthorhombic space group Pnma (No. 62), a = 7.023(4) Å, b = 13.309(7) Å, c = 14.294(7) Å, V = 1336(2) ų, Z = 4, R = 5.02%, and R_w = 5.24% for 1238 observed reflections [I > 3σ(I)]; for K₃(VO)(HV₂O₃)(PO₄)₂(HPO₄), M_r = 621.04, orthorhombic space group Pnma (No. 62), a = 6.975(3) Å, b = 13.559(7) Å, c = 14.130(7) Å, V = 1336(1) ų, Z = 4, R = 6.02%, and R_w = 6.34% for 1465 observed reflections [I > 3σ(I)].     

Luminescence properties of efficient X-ray phosphors of YBa3B9O18, LuBa3(BO3)3, α-YBa3(BO3)3 and LuBO3

The samples of YBa₃B₉O₁₈, LuBa₃(BO₃)₃, α-YBa₃(BO₃)₃ and LuBO₃ powders have been synthesized by the solid-state reaction methods at high temperature and their X-ray excited luminescent properties were investigated. All the studied materials show a broad emission band in the wavelength range of 300-550 nm with the peak centers at about 385 nm for YBa₃B₉O₁₈ and LuBa₃(BO₃)₃, 415 nm for α-YBa₃(BO₃)₃ and 360 nm for LuBO₃ powders, respectively. Even though those compounds have the different atomic structures, they have the common structural feature of each yttrium or lutetium ion bonded to six separate BO₃ groups, i.e., octahedral RE(BO₃)₆ (RE=Lu or Y) moiety. This octahedral RE(BO₃)₆(RE=Lu or Y) moiety seems to be an important structural element for efficient X-ray excited luminescence of those compounds, as are the edge-sharing octahedral TaO₆ chains for tantalate emission.     

The molecular structures of H2Os3(CO)10, H(SC2H5)Os3(CO)10 and (OCH3)2Os3(CO)10

X-ray crystallographic analyses of H₂Os₃(CO)₁₀, H(SC₂H₅)Os₃(CO)₁₀ and (OCH₃)₂Os₃(CO)₁₀ are reported. Although hydrogen atom positions have not been located, the essential isostructural nature of the three commplexes establishes the hydride ligands as bridging two metal atoms, separated by 2.670 Å, with a formal bond order of two; the bridging hydrido- and thiolato-ligands span an osmium---osmium bond of length 2.863 Å and formal bond order one; the two μ-methoxy ligands bridge two metal atoms separated by 3.078 Å which, by simple 18 electron rule counting, has a metal---metal bond order of zero. Some general comments are made on the structures of polynuclear transition metal carbonyls.     

Conductivities of the Ternary Systems Y(NO3)3+La(NO3)3+H2O, La(NO3)3+Ce(NO3)3+H2O, La(NO3)3+Nd(NO3)3+H2O and Their Binary Subsystems at Different Temperatures

Electrical conductivities were measured for the ternary systems Y(NO₃)₃+La(NO₃)₃+H₂O, La(NO₃)₃+Ce(NO₃)₃+H₂O, La(NO₃)₃+Nd(NO₃)₃+H₂O, and their binary subsystems Y(NO₃)₃+H₂O, La(NO₃)₃+H₂O, Ce(NO₃)₃+H₂O, and Nd(NO₃)₃+H₂O at (293.15, 298.15 and 308.15) K. The measured conductivities were used to test the generalized Young’s rule and the semi-ideal solution theory. The comparison results show that the generalized Young’s rule and the semi-ideal solution theory can yield good predictions for the conductivities of the ternary electrolyte solutions, implying that the conductivities of aqueous solutions of (1:3 + 1:3) electrolyte mixtures can be well predicted from those of their constituent binary solutions by the simple equations.