稀土-钛氧簇合物EuTi_6,EuTi_7和La_2Ti_(14)的可控合成（英文）

相比于纳米材料,原子精度的金属簇合物具有精确的表面结构和晶体结构,更有利于在原子水平上去理解化学反应的活性与结构的关系。作为团簇的一个有趣的分支,异金属的稀土-钛氧簇合物因其有趣的化学性质引起了人们的广泛关注。但是稀土-钛氧簇合物的精准合成是目前的重要挑战,这阻碍了其性能的进一步研究。因为螯合配体可以降低Ti~(4+)的水解速度,因此选择合适的螯合配体是制备稀土钛氧团簇的有效方法。最近,我们以螯合作用较强的3,5-二叔丁基水杨酸(H_2dtbsa)为配体,稀土盐和Ti(O~iPr)_4为原料,通过溶剂热法成功合成了四个新的稀土-钛氧簇合物[EuTi_6(μ_3-O)_3(OC_2H_5)_8(dtbsa)_6(Hdtbsa)]·(C_2H_5OH)(1),[EuTi_7(μ_3-O)3(μ_2-OH)_2(OiPr)_9(dtbsa)_6(Hdtbsa)Cl]·(HO~iPr)_3(2),[EuTi_7(μ_3-O)_3(μ_2-OH)_2(OiPr)_8(dtbsa)_7(Hdtbsa)]·(HOiPr)_2 (3)和[LaTi_7(μ_3-O)_3(μ_2-OH)_2(OC_2H_5)_8(dtbsa)_7(Hdtbsa)]_2·(C_2H_5OH)_4 (4)。单晶分析表明,七核化合物1内核EuTi6具有三角棱柱的结构,其中Eu3+位于六个Ti~(4+)离子形成的棱柱中心。八核化合物2和3的金属内核结构可以看作是化合物1中三棱柱的一侧连接一个Ti~(4+)。化合物4中,Ln_2Ti_(14)的金属骨架可看作是EuTi_7的二聚体。紫外-可见漫反射光谱估算的带隙值表明,簇合物1、2和3的禁带宽度值分别为2.35、2.07和2.16 eV,明显小于锐钛矿的禁带宽度值。光电响应测试发现这三种簇合物具有明显的光电响应,而且簇合物1和2的电荷分离效应好于簇合物3。为了探索这类簇合物在光催化方面的应用,我们做了在甲醇水溶液中的光催化(300–800 nm)分解水产氢实验。簇合物1、2和3的产氢率分别为112、106和87μmol?h~(-1)?g~(-1),高于商用P25。粉末X射线衍射(PXRD)和热重分析(TGA)证明了簇合物的光热稳定性。本文不但提供了一种制备稀土钛氧簇合物的螯合配体策略,而且还表明稀土钛氧簇合物具有较低的带隙和光驱动的催化活性。     

一例含有八核钴簇的锗钨酸盐的合成、结构及性质

以K_8Na_2[A-α-Ge W_9O_(34)]·25H_2O,Co(NO_3)_2·6H_2O和K_2CO_3等为原料,利用常规水溶液法合成了一例基于三缺位Keggin型多金属氧簇{Ge W_9O_(34)}的高核过渡金属衍生物K_(10.5)Cs_4H_(1.5){[Co_8(OH)_6(H_2O)_2](CO_3)_3(Ge W_9O_(34))_2}·12H_2O(1),并通过红外光谱、元素分析、热重分析和X射线单晶衍射等分析手段对其进行了表征。化合物1含有一个V型的多酸阴离子簇{[Co_8(OH)_6(H_2O)_2](CO_3)_3(Ge W_9O_(34))_2}~(16-),该阴离子进一步通过K~+和Cs~+离子连接形成二维结构。磁学性质研究表明,化合物1中Co~(2+)离子之间主要为反铁磁性耦合。     

过氧根桥连双核稀土化合物的制备及其磁/光响应行为研究

席夫碱还原后配体H_2L与Dy(ClO_4)_3或YbCl_3反应得到的晶体产物经过X射线单晶衍射数据分析表明,产物分别为过氧根桥连的双核稀土化合物[Dy_2(μ-O_2)L_2]·4MeOH·2H_2O(1)和[Yb_2(μ-O_2)L2]·3MeOH·2H_2O(2)。变温直流磁化率曲线(χMT-T)以及不同温度下磁化强度与磁场关系曲线(M-H)表明1有显著的磁各向异性,2存在较强的反铁磁相互作用。1000Oe外场下化合物1不同频率的变温交流磁化率曲线出现峰值,说明1为潜在的单分子磁体,通过ln(χ″M/χ'M)对T-1作图估算出其"能垒高度"约为6.1K,指前因子τ0≈2.4×10~(-6)s。荧光光谱测量发现1和2都具有配体L2-自身发光和稀土离子的特征发光。     

基于3,5-二(氧乙酸基)苯甲酸构建的多核锰(Ⅱ)配位聚合物的合成、晶体结构和氧化-还原性质（英文）

采用1,3-二(4-吡啶基)丙烷为模板剂,水热法合成了3个以3,5-二(氧乙酸基)苯甲酸(H_3BOABA)为配体的多核Mn(Ⅱ)配位聚合物:{(H_3O)[Mn_4(BOABA)_2(OH)_3(H_2O)]·H_2O}n(1),{(H_3O)_4[Mn7(BOABA)_4(OH)_6(H_2O)_2]}n(2),{(H_3O)_4[Mn_7(BOABA)_4(OH)_4(Cl)_2(H_2O)_2]·2H_2O}n(3)。通过X射线衍射,元素分析、红外光谱和热重分析进行了结构表征。结构分析表明,1为正交Pbcm空间群,由四核锰簇单元[Mn_4(μ3-OH)_3(COO)_(10)]构成具有(5,12)-连接的3D网络结构,拓扑符号为(32.47.5)2(38.423.514.621)。配位聚合物2与3为异质同构化合物,属正交Ccma空间群,分别由七核锰簇单元[Mn_7(OH)_6(COO)_(16)]和[Mn_7(OH)_4Cl_2(COO)_(16)]构成的具有(3,12)-连接的2D网络结构,拓扑符号为(43)4(430.624.812)。测定了聚合物的氧化-还原电位。     

3d-4f异金属修饰的缺位Lindqvist型同多酸化合物的合成与表征

在水热条件下,成功合成了一例新的异金属修饰的有机-无机杂化型多金属同多酸簇合物[Cu(en)_2(H_2O)]_4[Ce(W_5O_(18))_2]·4H_2O(1)(en=乙二胺),采用X射线单晶衍射、元素分析、X射线粉末衍射及热重分析对化合物进行了结构分析和基本表征.化合物1属于单斜晶系,P2_1/c空间群,单胞参数为a=2.736 1(2)nm,b=1.452 52(7)nm,c=1.634 53(9)nm,β=97.153(6)°.结构解析表明,化合物1中的中心离子Ce~(4+)与两个同多酸簇块的O原子结合形成八配位的四方反棱柱体,并通过游离的及支撑的[Cu(en)_2(H_2O)]~(2+)进行修饰.值得注意的是,化合物1是首例基于{W_5O_(18)}型同多酸簇块的Cu-Ce异金属修饰型有机-无机杂化的孤立结构.     

多孔金属有机骨架[Cd_3(PA-BIM)_6(BF_4)_6]·34H_2O的结构与可逆吸附的三维水簇网络

利用配体1,1-二[2-(苯基偶氮基)-1-咪唑基]甲烷(PA-BIM)与Cd(BF4)2作用,溶液扩散法得到了一个包结三维水簇网络的三维金属有机骨架化合物[Cd_3(PA-BIM)_6(BF_4)_6]·34H_2O(1)。晶体结构表明:金属镉以四面体方式同四个配体PA-BIM的反式构象配位,形成了一个三维的多孔金属有机阳离子骨架结构,多孔的结构中包结一个具有高度对称的三维水簇网格分子,具有由"书本型"构象六员水环与五员水环相互稠环而成的呈笼状结构(H_2O)_(14)簇单元,呈现液态水的结构特征。红外光谱、X-射线粉末衍射及热重分析结果均表明三维水簇分子具有可逆吸附性质,且三维水簇分子与金属有机阳离子骨架没有经典的氢键作用。     

一例反三棱柱型稀土四核MOF的合成、结构及性质研究

由5-咪唑间苯二甲酸(H_2L, C_(11)H_8O_4N_2)和稀土硝酸盐Er(NO_3)_3·5H_2O合成了一例具有单晶结构的三维稀土金属有机框架(MOF)材料,并通过元素分析、热重分析和X射线单晶衍射等确定了产物的组成和结构。结构分析表明:该晶体属于正交晶系,空间群为Imma,分别包含两种四核簇次级构筑单元,而其中的镧系金属离子分别呈七配位及八配位构型。     

基于1,2-丙二胺配体构筑Cu~Ⅱ-La~Ⅲ异金属修饰型磷钨酸化合物的合成与表征（英文）

在水热条件下,成功合成了一例新的Cu-La异金属修饰的有机-无机杂化型多金属磷钨酸簇合物[Cu(dap)_2]_(3.5)[Cu(dap)_2(H_2O)]_2[La(α-PW_(11)O_(39))_2]·6H_2O(1)(dap=1,2-丙二胺),并通过元素分析、红外光谱、热分析和X射线单晶衍射对化合物进行了表征和研究.结构分析表明在化合物1中,单稀土取代的二聚[La(α-PW_(11)O_(39))_2]~(11-)单元之间通过[Cu(dap)_2]~(2+)阳离子连接,形成一维Z字型链状结构.值得注意的是,化合物1是首例一维含1,2-丙二胺有机配体Cu-La异金属修饰的磷钨酸簇合物.     

混合配体构筑的两个锌(Ⅱ)和镉(Ⅱ)的金属有机框架化合物的合成、晶体结构及吸附和荧光性质（英文）

在溶剂热条件下,由1,3,5-三(1-咪唑基)苯(tib)和3,4′,5-联苯三羧酸(H_3BPT)或1,3,5-三(4-羧基苯基)苯(H_3BTB)与镉的硝酸盐或锌的硝酸盐反应,得到2个新的金属有机框架化合物[Cd_3(tib)_2(BPT)_2(H_2O)_2]·DMA·6H_2O(1)和[Zn_2(tib)(HBTB)_2(H_2O)]·2H_2O(2),并对其结构和吸附及荧光性能进行了研究。结构分析结果表明配合物1是一个具有4节点的三维框架化合物,其简化后的拓扑符号为{8~3}_4{8~5·12}{8~6}_2;而2是一个具有二维网格结构的化合物,该二维网格结构可进一步通过氢键作用形成三维超分子化合物。气体和蒸汽吸附性能研究结果表明1和2都可以选择性吸附CO_2和Me OH,荧光性能研究结果表明,1可以通过荧光猝灭机理在甲醇、乙醇、2-异丙醇、乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃、三氯甲烷、二氯甲烷和丙酮的混合溶剂中选择性识别丙酮分子。     

锌(Ⅱ)配合物的超分子设计及对甲醇蒸气的吸附性能

采用饱和蒸气扩散技术,将2,4-二羟基苯甲醛缩异烟酰腙(H_2dhbi)配体分别与Zn(ClO_4)2·6H_2O和Zn(NO_3)_2·6H_2O进行配位作用,得到2种不同配位模式的金属-有机框架材料[(dhbi)_2Zn_2·8H_2O]n(1)和{[(dhbi)_2(H_2O)_2Zn_2]·4DMF]}n(2).利用X射线单晶衍射、热分析技术(TG-DTA)和X射线粉末衍射(PXRD)等方法进行了结构表征.进一步将配位聚合物1和2用于对甲醇分子的吸附性能研究,结果表明,化合物1是一种理想的微孔材料,其对甲醇分子的吸附能力为化合物2的近5倍,采用PLATON对材料的孔隙体积进行计算得到化合物1和2的孔隙率分别为38.2%和5.5%.     

Synthesis, Structures, Fluorescence and Magnetism of Two Lanthanide Metal-organic Frameworks with CaF2 Topology Based on Silicon-centered Tetrahedral Ligand

Two 3D multifunctional lanthanide metal-organic frameworks(MOFs), Pr(HTCPS)(H₂O)·2DMF·C₂H₅OH· 5H₂O(JUC-93) and Pr₃(TCPS)₂(NO₃)(H₂O)₄(DMA)₂·2DMA·C₂H₅OH·3H₂O(JUC-94)[H₄TCPS=tetrakis(4-carboxyphenyl)- silane, DMF=N,N'-dimethylformamide, DMA=N,N'-dimethylacetamide and JUC=Jilin University China] were synthesized by the self-assembly of a rigid silicon-centered tetrahedral carboxylate ligand H₄TCPS and Pr(III) ions in different solvothermal reactions. X-Ray crystallography revealed that they exhibited a rare CaF₂ topology framework, constructed from the 4-connected tetrahedral TCPS unit with the 8-connected dinuclear praseodymium cluster unit and trinuclear praseodymium cluster unit, respectively. In addition, the luminescent and magnetic properties of the two compounds were investigated.     

Assembly of Two Isostructural Metal-organic Frameworks Based on Hetero-N,O Donor Ligand for Detecting Nitro Explosives

Two isostructural metal-organic frameworks,[NO3][M3(H2O)3O(TBA)3]-2DMF-6H2O(1 and 2)[M=In and Fe, H2TBA=4-(1H-tetrazol-5-yl)-benzoic acid], have been successfully synthesized. Compounds 1 and 2 have three-dimensional structures bridged via the typical 6-connected tri-nuclear cluster units M3O(COO)6 and linear linker H2TBA. The whole 3D framework possesses a 6-connected acs topology. Notably, by the fluorescence technique, compound 1 can detect nitro explosives through fluorescence quenching effect, especially for 2,4,6-trinitrophenol(TNP, Ksv=3.64×10^4 L/mol). Furthermore, the fluorescence spectrum red shifts as the number of NO2 group increases. Based on the aforementioned consideration, compound 1 can be considered as a potential luminescent probe for the detection of TNP.     

锌(Ⅱ)配合物的超分子设计及对甲醇蒸气的吸附性能

采用饱和蒸气扩散技术, 将2,4-二羟基苯甲醛缩异烟酰腙(H₂dhbi)配体分别与Zn(ClO₄)₂·6H₂O和Zn(NO₃)₂·6H₂O进行配位作用, 得到2种不同配位模式的金属-有机框架材料[(dhbi)₂Zn₂·8H₂O]_n(1)和{[(dhbi)₂(H₂O)₂Zn₂]·4DMF]}_n(2). 利用X射线单晶衍射、 热分析技术(TG-DTA)和X射线粉末衍射(PXRD)等方法进行了结构表征. 进一步将配位聚合物1和2用于对甲醇分子的吸附性能研究, 结果表明, 化合物1是一种理想的微孔材料, 其对甲醇分子的吸附能力为化合物2的近5倍, 采用PLATON对材料的孔隙体积进行计算得到化合物1和2的孔隙率分别为38.2%和5.5%.     

新型磷-钒-氧层状化合物[H2en]2[H3O]6[Co(H2O)2(VO)8(OH)4(PO4)8]的水热合成与晶体结构

金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1～5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].     

Crystal Structure and Photoluminescence Properties of Two Barium(Ⅱ) MOFs

In this article, two Ba(Ⅱ) metal-organic frameworks(MOFs), {[Ba(BPS)(H₂O)₂]·H₂O}_n(1) and[Ba(BPS)(H₂O)₂]_n(2)(H₂BPS=4,4'-bibenzoic acid-2,2'-sulfone), were synthesized and characterized. X-Ray crystal structural analyses reveal that compounds 1 and 2 have different structures, which is probably related to different coordination modes of ligand in compounds 1 and 2. It is remarkable that compounds 1 and 2 both show excellent thermal stability. The solid-state emission spectra reveal that compounds 1 and 2 both present strong luminescence emission bands at room temperature.     

溶剂控制的铜基金属-有机框架物的合成与荧光性能

金属-有机框架物在荧光识别领域表现出良好的应用前景,为探究合成更为精确识别的物质,本文利用二羧酸配体(H_2PAIA=5-丙酰胺基间苯二甲酸)和硝酸铜通过溶剂调控合成了两例结构不同的铜基金属-有机框架物(MOFs){[Cu(PAIA)(H_2O)]·2H_2O}(1)和{[Cu_3(PAIA)_2(DMSO)(Pyridine)_(1.5)]}(DMSO:二甲基亚砜;Pyridine:吡啶)(2)。尽管由相同的金属离子和有机配体构筑而成,但显示出具有显著溶剂导向特征的不同框架结构:配合物1为三维NbO型拓扑结构,而配合物2为二维sql型拓扑结构。正是由于这些结构上的差异,导致两个配合物的荧光识别性能和疏水性能展现出显著的不同。配合物1能够同时识别Pb~(2+)和Ag~+离子,而配合物2只能识别Pb~(2+),对Ag~+没有明显的信号响应。配合物1的疏水角85.06°比配合物2的52.71°有显著的增加。     

Solvothermal Synthesis, Structural Characterization and Properties of Two New Layered Lanthanide Sulfates

Two new layered lanthanide sulfates,[C₁₀H₁₀N₂][Pr₂(SO₄)₄(H₂O)₂](1)and[H₅O₂][Sm(SO₄)₂(H₂O)₃](2)were synthesized via solvothermal reaction and structurally characterized by single-crystal X-ray diffraction(XRD), infrared(IR) spectroscopy, thermal analysis, fluorescent spectra and inductively coupled plasma(ICP). Crystal data for compound 1, triclinic, P space group, a=0.8052(4) nm, b=0.9438(4) nm, c=1.4990(7) nm, α=79.450(5)°, β= 83.703(5)°, γ=74.048(5)°, V=1.0746(9) nm³, Z=2; for compound 2, monoclinic, P2₁/c space group, a=0.6599(11) nm, b=1.8940(3) nm, c=0.8765(14) nm, β=96.596(2)°, V=1.0883(3) nm³, Z=4. Structure analysis indicates that both the compounds exhibit a 2D corrugated layer structure, with protonated 4,4'-bipyridine cations and water dimmers (H₅O₂)⁺ located between the inorganic layers of compounds 1 and 2, respectively. Luminescent properties of compounds 1 and 2 were further investigated.     

Hydrothermal synthesis, crystal structures and luminescent properties of two new Ln(III)–succinate (Ln=Eu, Tb) complexes exhibiting three dimensional networks

Two new coordination polymers, [Eu₂(L)₃(H₂O)₂]_n 1 and {[Tb₂(L)₃(H₂O)₂]·H₂O}_n 2, (H₂L=succinic acid) have been synthesized by the reaction of H₂L with nitrate salts of Eu(III) or Tb(III) under hydrothermal conditions. The X-ray diffraction analysis reveals that the two complexes are constructed by L bridging the chains of edge-sharing EuO₈(H₂O) or TbO₈(H₂O) polyhedra to form 3D network structure. 1 and 2 possess different topological structures due to the difference in the conformations of L. The solid photoluminescence of 1 and 2 was also investigated in room temperature.     

Large heteropolymetalate complexes formed from lanthanide (Y, Ce, Pr, Nd, Sm, Eu, Gd), nickel cations and cryptate [As4W40O140]: synthesis and structure characterization

A new family of heteropolytungstate complexes (NH₄)₂₁[Ln(H₂O)₅{Ni(H₂O)}₂As₄W₄₀O₁₄₀]·xH₂O(Ln=Y, Ce, Pr, Nd, Sm, Eu, Gd) were prepared by the reaction of Na₂₇[NaAs₄W₄₀O₁₄₀]·60H₂O with NiCl₂·6H₂O and Ln(NO₃)₃·xH₂O at pH≈4.5. The crystal structures of (NH₄)₂₁[Gd(H₂O)₅{Ni(H₂O)}₂As₄W₄₀O₁₄₀]·51H₂O was determined by X-ray diffraction analysis and element analysis. The compound crystallizes in the monoclinic space group P2₁/n with a=19.754(3), b=24.298(4), c=39.350(6) Å, β=100.612(3)°, V=18564(5) ų, Z=2, R1(wR₂)=0.0544(0.0691). The central site S1 and two opposite sites S2 of the big cyclic ligand [As₄W₄₀O₁₄₀]²⁸⁻ are occupied by one Ln³⁺and two Ni²⁺, respectively, each site supply four O_d coordinating to metal ion, another one water molecule and other five water molecules coordinate, respectively, to Ni²⁺and Ln³⁺. Polyanion [Ln(H₂O)₅{Ni(H₂O)}₂As₄W₄₀O₁₄₀]²¹⁻ has C_2v symmetry. IR and UV–vis spectra of [NaAs₄W₄₀O₁₄₀]²⁷⁻ of the title compounds are discussed.     

Third-order Optical Nonlinearities of a Series of Compounds Derived from a Keplerate Type Molybdenum-oxide-based Polyoxometalate

Abstract By reacting the unique Keplerate type molybdenum-oxide based polyoxometalate （NH4）42·[MoI320372·（CH3COO）30（H2O）y2]·ca.300H2·ca. 10CH3COONH4（1） with tetramethylammonium bromide, a new derivative （NH4）26[TMA]16{MoI32O372（H2O）72（CH3COO）30}·ca.7NH4CH3COO·ca.189H2O（2, TMA=tetramethylammonium） was prepared. Compound 2 was characterized by Fourier transform infrared spectroscopy（FTIR）, UV-Vis, elemental and thermogravimetric analyses. By the well-established Z-scan technique, investigations on the nonlinear opti- cal（NLO） properties of the series of compounds derived from the Keplerate type molybdenum-oxide-based poly- oxometalate, namely, the newly prepared compound 2, the three previously reported compounds, included compound 1, （NH4hs（TBA）24{Mo132O372（H2O）72（CH3COO）30}·ca.7NH4CH3COO·ca. 173H2O（3, TBA=tetrabutylammonium） and （DODA）40（NH4）2[（H2O）nMo132O372（CH3COO）3o（H20）72]（4, DODA=dimethyldioctadecylammonium）, reveal that the third-order nonlinearity[x（3）] values of compounds 1, 2 and 3 in the DMF/H2O solution and compound 4 in chloro- form are almost the same, which indicates that the counter cations with different length of alkyl chains show ignora- ble impacts on the NLO susceptibility. In other words, the remarkable third-order nonlinearities[x（3）≈10 19 m2/V2] mainly come from the [MoI32O372（CH3COO）30（H2O）72]42 anions. This fact reveals that the applications of the NLO active polyoxometalates in various environments（such as hydrophilic, hydrophobic, polar, apolar, etc.） can be achieved by simply varying cations to meet the demands in the design of diverse devices. Keywords Keplerate type polyoxometalate; Nonlinear optical property; Z-Scan technique; Self-defocusing; Reverse saturable absorption