八钼酸根阴离子有机胺化合物的合成与结构

由MoO3和(CH3)3N或(C2H5)3N反应合成了两种分子组成分别为[(CH3)3NH]4Mo8O26·2H2O(1)和[(C2H5)3NH]4Mo8O26·2H2O(2)的化合物.单晶X衍射结构分析表明,化合物(1)属三斜晶系,空间群为P1,晶胞参数a=1.0500(2)nm,b=1.0533(2)nm,c=1.0765(2)nm,α=100.21(3)°,β=101.93(3)°,γ=118.47(3)°,V=0.9698(3)nm3,R1=0.0524.化合物(2)属单斜晶系,空间群为P21,晶胞参数a=1.1512(2)nm,b=1.3097(3)nm,c=1.7610(4)nm,β=101.40(3)°,V=2.6028(9)nm3,R=0.0428.结构分析表明,两种化合物中Mo8O264-阴离子均发生畸变,有机阳离子增大,Mo-O键键长缩短,阴离子畸变增大.     

新颖的咪唑官能化夹心型钨铋酸盐超分子化合物的合成与晶体结构

在常规条件下合成了一个新颖的超分子化合物Na8H[{Na(H2O)}3{Mn(C3H4N2)}3(BiW9O33)2]·32H2O, 通过X射线单晶结构分析、红外光谱及元素分析对该化合物进行了表征. 结果表明, 该化合物属六方晶系, P6(3)/m空间群. 晶胞参数a=1.394 8(4) nm, b=1.394 8(4) nm, c=3.348 6(19) nm, γ=120°, V = 5.641(4) nm3, Z=12. 该化合物是以α-B-BiW9钨铋酸盐为基本构筑单元的夹心结构化合物. 夹层中心3个Mn2+分别与3个咪唑分子配位形成无机-有机杂化材料. 3个[{Na(H2O)}3{Mn(C3H4N2)}3(BiW9O33)2]9-多阴离子结构基元利用氢键(非典型氢键)沿ab面构筑成具有三角形空穴的二维层状骨架结构. 这种二维层状结构利用氢键作用沿c轴方向交错排列, 形成了含有一维六边形孔道的三维超分子结构.     

新颖的(4,4’-bipy){[Ag(4,4’-bipy)]3[PMo12ⅥO40]}·H2O三维超分子多金属氧酸盐的合成和晶体结构

利用H3PMo12O40·4H2O, 4,4’-bipy和AgNO3反应, 在中温水热条件下合成了一种新颖的三维超分子多金属氧酸盐 (4,4’-bipy){[Ag(4,4’-bipy)]3[PMo12ⅥO40]}·H2O(1), 并通过元素分析、红外光谱、热重分析和X射线单晶衍射对其结构进行了表征. 结果表明, 该化合物属三斜晶系, P1空间群, 晶胞参数a=1.1275(2) nm, b=1.1910(2) nm, c =1.2898(3) nm, α = 112.63(3)°, β=94.63(3)°, γ=99.53(3)°, V=1.5567(5) nm3, Z=1. 该化合物具有三维超分子结构及荧光性质.     

新型有机-无机杂化材料(C3H5N2)4·PMoⅤMoⅥ11O40·4DMF·2H2O的合成、结构及抗前列腺癌活性研究

制备了有机-无机杂化材料(C3H5N2)4PMoⅤMoⅥ11O40*4DMF*2H2O. 用元素分析、红外光谱和X射线衍射对其进行了表征, 该晶体属三斜晶系, P1空间群, 晶胞参数为a=1.242 3(3) nm, b=1.266 6(3) nm, c=1.334 1(3) nm, V=1.742 3(6) nm3, α=70.56(3)°, β=71.16(3)°, γ=64.18(3)°, Z=1, R1=0.058 5, wR2=0.188 5. 结构解析表明, 十二钼磷酸阴离子和质子化的咪唑分子通过静电引力和氢键相互作用. 采用MTT法, 对其体外抗前列腺癌活性及毒性进行了研究.     

新型环形聚阴离子[{WO(H_2O)}_3(AsW_8O31)_3]~21-的结构及表征

在pH=3.0的水溶液中，Na_2WO_4·2H_2O与NaAsO_2·6H_2O和NH_4Cl反应，得 到了新的杂多钨酸盐(MH_4)_19Na_2[{WO(H_2O)}_3(AsW_8O31)_3]·45H_2O单晶， 用X射线单晶衍射法及元素分析确定了其结构，晶体属单斜晶系，空间群C2/c，晶 胞参数为：a=3.1165(11)nm, b=1.7388(7)nm, c=2.2789(9)nm, β=97.342(6)°, V=12.248(8)nm~3, Z=4, R_1=0.0571,wR_2=0.0741[I＞2σ(I)]. 环型聚阴离子 [{WO(H_2O)}_3(AsW_8O31)_3]~21-是由三个{WO(H_2O)}桥连三个新发现的 {AsW_8O31}单元构成的，环聚离子[{WO(H_2O)}_3(AsW_8O31)_3]~21-具有近似D_ (3h)对称性。对该化合物还进行了~183W NMR, IR和TG表征。     

同多化合物[C6H5CH2NH(CH3)2]4[Mo8O26]·4H2O的合成与晶体结构

以MoO3和C6H5CH2N(CH3)2为原料,制得[C6H5CH2NH(CH3)2]4[Mo8O26]·4H2O,并通过扩散法得到无色透明晶体.X射线单晶衍射表明,晶体属三斜晶系,空间群为P墿,晶胞参数a=1.0685(2)nm,b=1.4050(3)nm,c=1.0643(2)nm,α=93.12(3)°,β=110.26(3)°,γ=71.41(3)°,V=1.4179(5)nm3,R=0.0383.     

两个具有相似{V10}狚阴离子骨架的化合物的合成和结构表征

本文描述了两个具有相似阴离子骨架的化合物,犤Na2(H2O)10(NH4)4犦犤V10O28犦(1)和犤Na2(H2O)10(NH4)4犦犤V9MoO28犦(2)。化合物1的阴离子是一个常见的钒十骨架,而化合物2与化合物1是同晶异质体,化合物2的阴离子是混有一个钼原子的钒十骨架。X-射线晶体结构测定表明,这两个化合物均属于三斜晶系,P1珔空间群。晶胞参数分别为化合物1:a=0.86024(4)nm,b=1.04561(5)nm,c=1.12828(4)nm,α=68.833(1)°,β=87.158(1)°,γ=67.065(1)°;化合物2:a=0.86511(3)nm,b=1.04549(5)nm,c=1.12446(5)nm,α=69.071(1)°,β=87.145(1)°,γ=66.982(1)°。     

两个具有相似（V10）阴离子骨架的化合物的合成和结构表征

本文描述了两个具有相似阴离子骨架的化合物,[Na2(H2O)10(NH4)4][V10O28](1)和[Na2(H2O)10(NH4)4][V9MoO28](2).化合物1的阴离子是一个常见的钒十骨架,而化合物2与化合物1是同晶异质体,化合物2的阴离子是混有一个钼原子的钒十骨架.X-射线晶体结构测定表明,这两个化合物均属于三斜晶系,P1空间群.晶胞参数分别为化合物1a=0.86024(4)nm,b=1.04561(5)nm,c=1.12828(4)nm,α=68.833(1)°,β=87.158(1)°,γ=67.065(1)°;化合物2a=0.86511(3)nm,b=1.04549(5)nm,c=1.12446(5)nm,α=69.071(1)°,β=87.145(1)°,γ=66.982(1)°.     

金属-氧簇支撑的过渡金属配合物[{Ni(phen)_2}_2(ξ-Mo_8O_(26))]的水热合成、结构及量子化学研究

以MoO3, H2MoO4, Ni(OAc)2·6H2O 和 1, 10-邻菲咯林(1, 10-phen)为原料, 用水热法合成出了八钼氧酸盐支撑的镍-邻菲咯啉配合物[{Ni(phen)2}2(ξ?Mo8O26)]. 化合物的晶体属于单斜晶系P21/n空间群, a = 1.2952(2), b = 1.6659(10), c = 1.3956(12) nm, ? =106.273(8)°, V = 2.8906(5) nm3, Z = 2. 由5604个可观测衍射(I ＞2? (I ))用于精修所有的结构参数, 得一致性因子R1 = 0.0414, WR2 = 0.0815. 结构测定结果表明, 化合物中的八钼氧酸盐具有新奇的前所未有的结构类型(称之为?-isomer), 其特点是它由Mo6O6环和环中两侧处于戴帽位置的2个MoO6八面体组成. Mo6O6环含有2个八面体配位的MoⅥ原子和4个三角双锥配位的MoⅥ原子. 每个?-[Mo8O26]4?结构单位通过Mo6O6环中八面体配位的Mo原子的端氧和相邻的三角双锥配位的Mo原子的端氧与2个[Ni(phen)2]2+单位相键合. 测定了化合物的IR和UV-Vis光谱, 并用EHMO方法对其电子结构进行了研究.     

[Nd(ONO2)6][Cu(Im)(Phen)2]2(OH)·4H2O的合成、晶体结构及磁性质

用Nd(NO3)3·6H2O、Im(C3H4N2)、Phen(C12H8N2)和Cu(NO3)2·3H2O为原料,两步反应合成了标题化合物.该化合物晶体属P1空间群,晶胞参数a=1.012 6(2) nm,b=1.179 2(2)nm,c=1.398 5 nm,α=111.32(3)°,β=93.17(3)°,γ=90.33(3)°,Z=1,R=0.043.测定了化合物的UV-Vis-NIR及IR光谱和变温磁化率,发现标题化合物在低温下具有反铁磁性质.     

Reactions inside a porous nanocapsule/artificial cell: encapsulates' structuring directed by internal surface deprotonations

In the cavities of unprecedentedly functionalised, spherical, porous capsules of the type {Pentagon}12{Linker}30 identical with [{(Mo)Mo5O21(H2O)6}12{Mo2O4(ligand)}30]n- reactions with the ligands -i.e. at the internal shell surfaces - can be performed, in the present case deliberate aquation/hydration and deprotonation reactions at the linker fragments {(Mo2O4)C2O4H}+ similar to that reported in the literature for [(NH3)5CoC2O4H]2+ in solution.     

X-ray Crystal Structure and Characterization of Tetra-vanadyl Capped Highly Reduced Polyoxometalate Anion[PmoⅥ5MoⅤ7O40(VⅣO)4]2-

A novel polyoxometalate [H3O]2[PmoⅥ5MoⅤ7O40(VⅣO)4]*6Py(Py=pyridine) was synthesized and characterized by IR spectrometry, TG and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic space group(C2/m) with a=1.3680(3) nm, b=2.1740(4) nm, c=1.1630(2) nm, β=118.62(3)°, V=3.0362(10) nm3, Z=2, and R1(wR2)=0.0772(0.2312). The compound contains a highly reduced vanadylpolymolybdophosphate polyoxometalate anion with a four-capped structure. The four {VO} units cap four opposite pits of the pseudo-Keggin core {PMo12O40}.     

钼钒氧簇二聚体[Ni(enMe)_2]_4{[Ni(enMe)_2][Ni(enMe)_2(H_2O)]_2[Mo_8~(Ⅵ)V_6~(Ⅳ)O_(38)(V~ⅤO_4)]_2}·8H_2O的合成与结构表征(英文)

在水热条件下合成了一例新型的多金属氧酸盐二聚物,[Ni(enMe)2]4{[Ni(enMe)2][Ni(enMe)2(H2O)]2[Mo8ⅥV6ⅣO38(VⅤO4)]2}.8H2O(1)(enMe=1,2-丙二胺),利用元素分析、红外光谱分析、粉末X射线衍射、热重分析和单晶X射线衍射表征了其结构。结果表明,化合物(1)属于单斜晶系,P2(1)/n空间群.晶胞参数为a=1.9685(4)nm,b=1.3549(3)nm,c=2.7039(5)nm,α=90°,β=93.94(3)°,γ=90°,V=7.195(2)nm3,Z=4,Dc=2.390g/cm3,Mr=2588.4,μ=3.195mm-1,F(000)=5012,最终R1=0.0743,wR2=0.1861.与此同时,(1)是第一个具有二帽-Keggin型钼钒氧簇的二聚体,它由过渡金属部分[Ni(enMe)2(H2O)]22+连接形成{[Ni(enMe)2][Ni(enMe)2(H2O)]2[Mo8ⅥV6ⅣO38(VⅤO4)]2}8-二聚阴离子.     

Structural varieties in heterobimetallic lanthanide disiloxanediolates: "inorganic metallocenes" versus in-plane metallacrowns

The previously proposed concept of "inorganic metallocenes" of group 3 and rare-earth elements has been tested by preparing a series of novel disiloxanediolates with metals displaying different ionic radii. For the smaller scandium and yttrium, approximately planar arrangements of the disiloxanediolate frameworks with solvent and chloride ligands in trans positions were found. Thus, the compounds [{(Ph2SiO)2O}2{Li(DME)}2]ScCl(THF/DME) (2; DME=1,2-dimethoxyethane and THF=tetrahydrofuran) and [{(Ph2SiO)2O}2{Li(THF)2}2]YCl(THF) (3) can be described as heterobimetallic inorganic ring systems or metallacrown complexes with "in-plane" coordination of the metal. In contrast, "out-of-plane" geometries with cis coordination of additional ligands were identified in the praseodymium derivatives [{(Ph2SiO)2O}2{Li(THF)2}{Li(THF)}]Pr(micro-Cl)2Li(THF)2 (4) and [{(Ph2SiO)2O}2{Li(DME)}2]PrCl(DME) (5). These compounds can be viewed as analogues of the known metallocene derivatives (C5Me5)2Pr(micro-Cl)2Li(THF)2 and (C5Me5)2PrCl(THF). The molecular structures of 2-5 have been determined by X-ray diffraction.     

两个新的Dowson结构硫钼多酸盐合成，表征以及催化性质

通过水热技术合成了两种新的Dowson结构硫钼多酸盐[C5N2H14]2[S2MoⅥ18O62].8H2O(1)和[C5N2H14]8(H3O)2[S2MoⅤ2MoⅥ16O62]3.(C5H5N)2(2),并通过X射线分析、红外光谱和元素分析其进行了表征。X射线晶体结果分析,化合物1结晶于正交晶系,Pmmn空间群,a=1.79929(17)nm,b=1.35804(13)nm,c=1.41926(13)nm,V=3.4680(6)nm3,Z=2。化合物2结晶于单斜晶系,C2/m空间群,a=2.266 5(3)nm,b=1.374 9(2)nm,c=3.291 2(5)nm,β=104.31(0)°,V=9.938(2)nm3,Z=4。化合物1和2都含有Dawson结构的硫钼多酸阴离子和质子化的N-甲基哌嗪阳离子。并且由苯乙烯的氧化催化结果中看出混价钼的化合物2的催化活性要比化合物1略高。     

Unusual inorganic ring systems of scandium and yttrium containing group 13 Metals: coordination of monomeric Me(2)InOMe to yttrium

Novel transformations of lanthanide(III) disiloxanediolates with group 13 metal trialkyls are reported. Treatment of the scandium metallacrown complex [{(Ph2SiO)2O}2{Li(DME)}2]ScCl.THF (1) with AlMe3 resulted in an Li-Al exchange reaction and the formation of the heterotrimetallic inorganic ring system [{(Ph2SiO)2O}2{Li(THF)2}AlMe2]ScCl.THF (2). The related yttrium metallacrown [{(Ph2SiO)2O}2{Li(THF)2}2]YCl.THF (3) reacts with InMe3 under the formation of the heterobimetallic Y/In disiloxanediolate complex [{(Ph2SiO)2O}2{InMe2(OMe)}2InMe2]Y (4). In the latter, two monomeric Me2InOMe ligands are stabilized through coordination to yttrium.     

咪唑配位的夹心型杂多化合物Na_9[{Na(H_2O)}_3{Co(C_3H_4N_2)}_3(BiW_9O_(33))_2]·33H_2O的合成，结构和磁性质研究

在pH=7.5的水溶液中，咪唑与Na_2WO_4,Bi(NO_3)_3及Co(NO_3)_2反应，得到 了咪唑配位的新型杂多钨酸盐Na_9[{Na(H_2O)}_3{Co(C_3H_4N_2)}_3(BiW_9O_(33) )_2]·33H_2O，用X射线单晶衍射法及元素分析确定了其结构，晶胞参数为：空间 群P3，a=1.3904(4)nm, b=1.3904(4)nm, c=3.3169(13)nm, γ=120 °,V=5.553(3) nm~3, Z=2, R_1=0.0361，wR_2=0.0507(I>2σ)。杂多阴离子[{Na(H_2O)_3}{Co (C_3H_4N_2)}_3(BiW_9O_(33))_2]~(9-)为夹心式结构，两个三空缺Keggin离子α- B-BiW_9O_(33)~(9-)夹层中的中心离子为交替排列的三个Na(H_2O)~+和三个Co (C_3H_4N_2)~(2+)，中心离子钴的配位数为5，该杂多阴离子具有C_(3v)对称性。 对标题化合物进行了磁性质表征，拟合结果为J=6.90cm~(-1),g=2.10,θ=0.25K， 表明该化合物中的Co(II)三核簇存在着铁磁偶合。     

N-对R苯基氮杂15冠5八钼多酸钠超分子配合物的合成与结构

为研究大环化合物对客体分子的选择性, 合成了通式为[NaL(Et2O)]2Na2Mo8O26的三种新型N-对R苯基氮杂15冠5八钼多酸钠超分子配合物(其中L分别为: N-苯基氮杂15冠5、N-对氯苯基氮杂15冠5和N-对甲苯基氮杂15冠5), 进行了元素分析, 红外光谱与核磁共振等结构参数的表征, 对R基为CH3的标题配合物作了X射线四圆衍射测定, 该晶体属单斜晶系, 空间群为P21/a,a=1.4590(4)nm, b=1.3817(3)nm, c=1.7639(5)nm, β=112.67(2)°, V=3.281(1)nm^3, Mr=2021.3, Dc=2.11g/cm^3,μ=2.37mm^-^1, F(000)=2048, R=0.045和Rw=0.057, 与[Na.(DB18C6)(CH3OH)M6O19和[Na(DB24C8)]2M6O19进行比较,结果表明: 大环化合物不仅对客体金属离子有分子识别性, 而且对与之抗衡的多酸阴离子也具有影响。     

Reactions of a {Mo16}-type polyoxometalate cluster with electrophiles: a synthetic, theoretical and magnetic investigation

A medium-nuclearity mixed-valence polyoxomolybdate [H2Mo16O52]10-={Mo16}(1a) was synthesized using an approach that employed protonated hexamethylenetetramine (HMTAH+) as counter ion and yielded (HMTAH)10 1a.34 H2O (1). The {Mo16} cluster anion exhibits significant nucleophilicity and traps electrophiles such as divalent transition metal ions, resulting in a family of isostructural compounds based on {Mo16M2}-type anions [M(H2O)8H2Mo16O52]6- (M=FeII (2), MnII (3), CoII (4)). The highly reactive nature of the {Mo16} system is also revealed by rearrangement and decomposition reactions of to either slowly form a sodium-bridged heptamolybdate-based chain compound (5) when left in the reaction solution or, in the presence of very high concentrations of electrophiles, to heptamolybdate-based cluster compounds [M2(H2O)9Mo7O24]2- of the {M2Mo7}-type (M=FeII (6), MnII (7)). Compounds were characterised by single crystal X-ray diffraction, elemental analysis, IR spectroscopy, magnetic susceptibility measurements, and density functional theory calculations.