Structure and Luminescence Property of a Hexanuclear Silver(I) Cluster Containing Pyridine-3-carboxaldehyde Thiosemicarbazone

A new hexanuclear silver（I） compound containing thiosemicarbazone with group of 3-pyridine was synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analysis and fluorescence spectrum.The title compound 3 crystallizes in monoclinic,space group C2/m with a = 18.6523（9）,b = 24.7519（11）,c = 22.4542（15） ,β = 93.4960（10）°,V = 10347.4（10）3,C68H104Ag6N30O8S6,Mr = 2309.39,Dc = 1.482g/cm3,μ（MoKα） = 1.293 mm-1,F（000） = 4656,Z = 4,the final R = 0.0544 and wR = 0.1580 for 6733 observed reflections（I 〉 2σ（I））.In the structure,two Ag6L36（L3 = pyridine-3-carboxaldehyde thiosemicarbazone） clusters are contained.In each cluster,the S atom of ligand L3 served as a triply bridged chelator to connect the six silver atoms into a Ag6L36 cluster.Luminescence investigation revealed that the band at 630 nm was attributed to cluster-centered（CC） electron transfer,and those at 493 and 530 nm to the LMCT and CC transitions,respectively.

Hydrothermal Synthesis and Crystal Structure of a Novel Hexanuclear Copper(Ⅱ) Complex:[Cu_6(DPPZ)_4(btc)_4(H_2O)_8]·5H_2O

A new hexanuclear copper（Ⅱ） complex,[Cu 6 （DPPZ） 4 （btc） 4 （H 2 O） 8 ]·5H 2 O （1,DPPZ=dipyrido[3,2-a：2,3-c]phenazine,H 3 btc=1,3,5-benzenetricarboxylic acid）,has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analyses,IR,and thermogravimetric analysis.Its crystal structure is of triclinic system,space group P1 with a=12.489（4）,b=14.234（5）,c=14.484（5）,α=82.848（4）,β=79.399（4）,γ=73.646（4）°,V=2421.2（13） 3,Z=1,Cu 6 C 108 H 78 N 16 O 37,M r=2573.17,D c=1.752 g/cm 3,μ=1.398 mm-1,F（000）=1308,GOOF=1.011,the final R=0.0495 and wR=0.1030 for 5420 observed reflections with I 2σ（Ⅰ）.In 1,four btc 3ligands act as bridges between six neighboring Cu atoms to form an unusual hexanuclear copper cluster.The clusters are further connected by two types of O-H···O and O-H···N hydrogen bonds,generating a three-dimensional supramolecular structure.In addition,intermolecular and intramolecular π-π stacking interactions further consolidate the three-dimensional supramolecular framework of 1.

Structure and Luminescence Property of a Hexanuclear Silver(Ⅰ) Cluster Containing Benzaldehyde Thiosemicarbazone

A new hexanuclear silver （I） compound 2 containing thiosemicarbazone with the group of benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound crystallizes in triclinic, space group P with a = 11.611（3）, b = 15.610（5）, c = 15.624（7） , α = 113.942（6）, β = 104.520（6）, γ = 104.230（4）°, V = 2304.1（14） 3, C60H77Ag6N22O4.5S6, Mr = 2018.02, Dc = 1.454 g/cm3, μ（MoKα） = 1.435 mm-1, F（000） = 1005, Z = 1, the final R = 0.0468 and wR = 0.1474 for 6608 observed reflections （I 2σ（I））. In the structure, the S atom of the ligand L2 （L2 = benzaldehyde thiosemicarbazone） served as a triply bridged chelator to connect the six silver atoms into a Ag6L26 cluster. The luminescence property of compound 2 was investigated at room temperature.

Structure and Luminescence Property of a Hexanuclear Thiosemicarbazone Silver(I) Cluster

A new hexanuclear silver（I） compound containing thiosemicarbazones with groups of 1-naphthalene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound crystallizes in monoclinic, space group P21/c with a = 16.101（4）, b = 24.855（7）, c = 14.492（4） A, β = 109.730（5）, V = 5459（3） A3, C90H102Ag6N2406S6, Mr= 2455.54, Dc= 1.494 g/cm3,μ（MoKa） = 1.228 mm^-1, F（000） = 2472, Z = 2, the final R = 0.0761 and wR = 0.1507 for 5258 observed reflections （I〉 2α（I））. In the structure, the S atom of ligand L serves as a triply bridged chelator to connect the six silver atoms into a Ag6L6 cluster. Luminescence investigation reveals that the compound exhibits two ligand-independent cluster-centered electron transfer bands and one ligand-dependent charge transfer band.

Crystal Structure of a Hexanuclear Silver（Ⅰ） Compound [Ag_6L^66]·4DMF and Luminescence Discussion of a Series of Silver（Ⅰ） Clusters

A new silver（Ⅰ） compound 6 （[Ag6L66]·4DMF） containing thiosemicarbazone with the group of 2-chloro-1-benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound 6 crystallizes in monoclinic, space group C2/c with a = 26.9236（18）, b = 15.2553（8）, c = 24.6237（13） , β = 103.0680（10）°, V = 9851.7（10）3, C58H66Ag6Cl6N20O3S6, Mr = 2143.59, Dc = 1.445 g/cm3, μ（MoKα） = 1.503 mm-1, F（000） = 4232, Z = 4, the final R = 0.0565 and wR = 0.1654 for 5831 observed reflections （Ⅰ 〉 2σ（Ⅰ））. Similar to the structure of the compounds we have reported, compound 6 also exhibits a hexanuclear silver（Ⅰ） cluster. In the cluster, the S atom of ligand L6 （L6 = 2-chloro-1-benzaldehyde thiosemicarbazone） served as a triply bridged chelator to connect the six silver atoms into a Ag6L66 cluster. The luminescence property of compound 6 was investigated at room temperature and compared with other similar compounds in order to find the factors influencing their luminescent property.

Synthcsis, Structure and Magnetochemistry of a New Hexanuclear Manganese Oxide Complex of the Formula [Mn_6O_2 (O_2CPh)_(10)(CH_3CN)_4]

The reported X-ray structure and magnetochemical properties of [Mn6O2 (OCPh)10, (CH3CN)4], effectively derived from [NBu4][Mn4O2(O2CPh)9 (H2O)] with equivalent of tren in CH3CN is shown.

A Copper(Ⅱ)-cadmium(Ⅱ) Heterometallic Hexanuclear Complex:[Cd_4Cu_2(pdc)_4(H_2O)_(14)](H_3pdc=3,5-Pyrazoledicarboxylic Acid)

The title complex 1,[Cd 4 Cu 2 （pdc） 4 （H 2 O） 14 ] （H 3 pdc=3,5-pyrazoledicarboxylic acid）,has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=0.67235（10）,b=1.27935（18）,c=1.28569（17） nm,α=112.633（2）,β=102.971（3）,γ=97.089（2）o,V=0.9673（2） nm 3,C 20 H 32 Cd 4 Cu 2 N 8 O 30,M r=1441.22,D c=2.474 g/cm 3,μ（MoKα）=3.356 mm 1,F（000）=698,S=1.003,Z=1,the final R=0.0471 and wR=0.0748 for I 2σ（Ⅰ）.In 1,two deprotonated 3,5-pyrazoledicarboxylic acids （pdc 3）,one copper（Ⅱ） ion and one cadmium（Ⅱ） ion firstly form a pyrazole-bridged Cu II Cd II dinuclear unit,two of which related by an inversion center are connected by another two cadmium（Ⅱ） ions through chelating carboxylate groups to construct the copper（Ⅱ）-cadmium（Ⅱ） heterometallic hexanuclear complexes.Plenty of hydrogen bond interactions existing in the system further lead to a three-dimensional （3D） supramolecular framework.

Synthesis, Structure and Comparison of Luminescent Property between Two Hexanuclear Silver(Ⅰ) Thiosemicarbazone Clusters

A new silver（Ⅰ） compound 4 containing thiosemicarbazone with group 2-quinoline was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. Compound 4 crystallizes in triclinic, space group P1 with a = 12.2710（9）, b = 16.9281（13）, c = 17.2984（13）, α = 112.8500（10）, β = 103.4890（10）, γ = 102.6860（10）°, V = 3020.9（4） 3, C80H94Ag6N28O6S6, Mr = 2383.41, Dc = 1.310 g/cm3, μ（MoKα） = 1.108 mm-1, F（000） = 1196, Z = 1, the final R = 0.0567 and wR = 0.1368 for 5112 observed reflections （I 〉 2σ（I））. Similar to the structure of compound 2 we have reported, compound 4 also exhibits a hexanuclear silver（Ⅰ） cluster. In the cluster, the S atom of ligand L4 （L4 = 2-quinolinecarboxaldehyde thiosemicarbazone） serves as a triply bridged chelator to connect the six silver atoms into a Ag6L46 cluster. The luminescence property of 4 is investigated at room temperature and compared with that of 2.

Synthesis and Structure of the Hexanuclear Diazenidooxomolybdate[（n—C

Compound[(n-C4H9)4N]3 [Mo6O18(N2C6H4-pNO2)] crystallizes in the orthorhombic space grou Pnma with a= 23. 964(9).b=16.948(4),c=17.968(7) A,V=7298(7) A3,Z=4,and Dc=1.58 g/cm-3. Structure solution and refinement based on 3113 reflections with I>3.0σ(I) gave final residuals of R= 0.072 and Rω=0.099.The anion is a substitution isopolymolybdate.

A Hexanuclear Cobalt Cluster with Tetracubane-like Topology: Synthesis, Structure and Magnetic Properties

One hexanuclear cobalt cluster [Co_(2) ^(Ⅲ)Co_(4) ^(Ⅱ)(L)_(4)(CH_(3) COO)_(2)(MeO)_(4)]·MeOH(1) was synthesized by the reaction of H_(2)L(H_(2)L=2-((2-hydroxy-4-methoxy-benzylideneamino)methyl)phenol) and Co(OAc)2·4 H2O in MeOH under solvothermal conditions. Complex 1 crystalizes in the triclinic space group P1 with a = 14.397(3), b = 16.625(3), c = 18.992(4) A, α = 109.47(3)°, β = 99.24(3)°, γ = 112.37(3)°, Dc = 1.464 g/cm^(3), Z = 2, V = 3741.7(2) A^(3), the final R = 0.0781 and w R = 0.1436 for 13051 observed reflections with I > 2σ(I). In the structure of 1, two cobalt ions are in 3+ oxidation states and four cobalt ions are in 2+ valence states. The six cobalt atoms are held together by six phenolate oxygen atoms from four L^(2–) ligands, four oxygen atoms from two chelating acetates and four μ3-O atoms from four Me O– groups. The six cobalt atoms are located at six corners of four defective cubanes. Thus, complex 1 displays tetracubane-like topology. Solid-state dc magnetic susceptibilities were measured for 1 in the 2.0~300 K range. Antiferromagnetic interactions were determined for 1.

Secondary Metal Coordination Using a Tetranuclear Complex as Ligand Leading to Hexanuclear Complexes with Enhanced Thermal Barriers for Electron Transfer

Postsynthesis of the paramagnetic square-shaped complex{[(Tp*Me)Fe(μ-CN)_(2)(CN)][Co(dmbpy)_(2)]}_(2)(BPh_(4))_(2)·6MeCN·H2O[1,Tp*Me=tris(3,4,5-trimethylpyrazole)-borate;dmbpy=4,4′-dimethyl-2,2′-bipyridine)]by grafting transition metal(II)thiocyanates via its terminal cyano groups afforded three hexanuclear[Fe_(2)Co_(2)M_(2)]clusters(M=Zn,2;Co,3;Cd,4).The peripheral metal-complex units serving as excellent electron acceptors were found to help stabilize the low-temperature state of Fe^(II,LS)–Co^(III,LS) within the complex core.

六核配合物［Mn_6O_2（O_2CPh）_（10）（py）_4］·MeCN的合成及结构

将［Ｍｎ３Ｏ（Ｏ２ＣＰｈ）６（ｐｙ）２（Ｈ２Ｏ）］·０．５ＭｅＣＮ、水杨醛缩邻氨基酚和三乙胺在乙腈溶液中反应，合成了六核锰配合物。经Ｘ射线单晶结构分析确定该配合物晶体的化学结构式为［Ｍｎ６Ｏ２（Ｏ２ＣＰｈ）１０（ｐｙ）４］·ＭｅＣＮ。结构中含有一个［Ｍｎ６Ｏ２］１０＋核，可看成是两个［Ｍｎ４（μ４－Ｏ）］四面体共一条边，每个四面体的中心是一个μ４－Ｏ２－离子。晶体属单斜晶系，Ｐ２１／ａ空间群，晶胞参数ａ＝２．０５７２ｎｍ，ｂ＝１．８５２０ｎｍ，ｃ＝２．５３７５ｎｍ，β＝１１１．８２°，Ｖ＝８．９７５ｎｍ３，Ｚ＝４，最终偏差因子Ｒ＝０．０６３２，Ｒｗ＝０．０５９５。

新法合成Cu_6(C_5H_4NS)_6簇合物及其性质

A hexanuclear copper（Ⅰ） cluster [Cu6(C5H4NS)6] was synthesized by means of the hydrothermal reaction of [Cu(PPh3)2（MeCN）2]ClO4 with（2-mercaptopyridine-1-oxide） in the presence of 2-butanol,Et3N and water and characterized by elemental analysis,IR,TGA and solid state fluorescence spectroscopy as well as X-ray diffractometry.The crystallographic data for the title complex,C15H12Cu3N3S3,are Mr=521.08,monoclinic space group P2（1）/n and the cell parameters are: a=0.958 59（6） nm,b=（1.604 85（12） nm）,（c=）0.122 712（10） nm,β=108.863（2）°,V=1.786 4（2） nm3,Z=4,Dc=（1.937 Mg/m3）,R1=0.030 1,ωR2=0.031 5（I>2σ（I））,F（000）=1 032,μ=3.890 mm-1,R（int）=0.050 1,S=0.598.The title complex exhibits highly thermal stability and strong low energy fluorescence（（λ=）744 nm） when it is irradiated by the light（λ=468 nm） in solid state at room temperature.

六核银簇合物Ag_6(Ph_3CCS_2)_6·Py·6DMF和单核银络合物Et_4N^+[Ag(Ph_3CCS_2)_2]^-·2THF的合成和晶体结构

用新合成法制备的新型配体三苯基乙荒酸四乙基铵盐(Ⅰ)和 AgNO_3在不同条件下反应分别获得单核银络合物Et_4N^+[Ag(Ph_3CCS_2)_2]^-·2 THF(晶体Ⅱ)和六核银簇合物Ag_6(Ph_3CCS_2)_6·Py.6DMF(晶体Ⅲ)。用X射线单晶衍射法测定了它们的晶体结构。

簇合物Co_6S_8(PBu_3~n)_6的晶体结构及簇骼M_6E_8P_6(E=S,Se,Te)的协同效应

簇骼为Ｍ６Ｅ８Ｐ６的六核簇合物的一个新成员——Ｃｏ６Ｓ８（ＰＢｕｎ３）６的合成和晶体结构表明，可能是由３个单核基元Ｃｏ（ＰＢｕｎ３）２Ｓ先组装成三核簇状基元化合物Ｃｏ３（μ２－Ｓ）３（μ３－Ｓ）（ＰＢｕｎ３）３，然后由２个这样的三核亚单元形成μ３－Ｓ桥生成该六核簇合物．讨论了簇骼为［Ｍ６Ｅ８Ｐ６］ｎ（Ｍ＝Ｆｅ，Ｍｏ，Ｃｏ，Ｃｒ，Ｗ；Ｅ＝Ｓ，Ｓｅ，Ｔｅ；ｎ＝－１，０，＋１，＋２，＋３）的系列簇合物的分子内协同效应．

脱水对六核锰单分子磁体磁性的影响

以水杨醛肟和Mn(CH3COO)2.4H2O为原料,合成了一个新的六核锰簇合物[Mn6O2(CH3COO)2(salox)6(H2O)4].10H2O(salox2-表示负二价的水杨醛肟),对其进行了单晶X射线衍射分析及脱水前后样品的直流和交流磁性测试。结果表明,该簇合物是一个反铁磁性单分子磁体,脱水使得六核锰簇内的反铁磁作用增强,磁弛豫能垒下降,但簇合物仍保持单分子磁体的性质。

六核钴羰基簇的P(OC_2H_5)_3取代衍生物的合成、表征与结构

用P(OC2 H5) 3 与母体簇Co6(μ6 P) (μ SCH2 CH2 CH2 S) (μ PSCH2 CH2 CH2 S) (CO) 12 进行取代反应得到一个二取代产物Co6(μ6 P) (μ SCH2 CH2 CH2 S) (μ PSCH2 CH2 CH2 S) (μ CO) (CO) 9[P(OC2 H5) 3 ]2 (Ⅰ ) ,同时还得到了两个一取代产物Co6(μ6 P) (μ SCH2 CH2 CH2 S) (μ PSCH2 CH2 CH2 S) (CO) 11[P(OC2 H5) 3 ](Ⅱa和Ⅱb ,Ⅱb是Ⅱa的一个同分异构体 ,其谱学数据与Ⅱa不同 ) .对合成的三个簇合物进行了元素分析、IR、1HNMR、3 1PNMR和MS谱学表征 ,对Ⅰ做了X射线单晶衍射测定 ,其晶体属于单斜晶系 ,P2 1/n空间群 ,晶胞参数 :a =1 1170 (2 )nm ,b =2 35 5 4(5 )nm ,c =1 7977(4 )nm ,β =99 5 0 (3)°,V =4 6 6 49(17)nm3 ,Z =4,Dc=1 76 3g/cm3 ,F(0 0 0 ) =2 488,μ =2 4 6 4cm-1.X射线晶体结构分析表明 ,取代位置发生在簇合物顶端的两个钴原子上 .晶体结构用直接法解出 ,经用全矩阵最小二乘法对原子参数进行修正 ,最后的偏离因子为R1=0 0 497,wR2 =0 1386 .

新型六核钼原子簇化合物｛〔Mo_3（μ_3－S）（μ－S_2）_2（dtp）_3

［Ｍｏ３（μ３－Ｏ）（μ－Ｓ）３（μ－ＯＡｃ（ｄｔｐ）３（ｐｙ）］和［Ｍｏ３（μ－Ｓ）３（μ－ＯＡｃ（ｄｔｐ）３－（ｐｙ）］（ｄｔｐ＝Ｓ２Ｐ（ＯＣ２Ｈ５）２＾－）族合物分别与金属化合物ＢｉＩ３和ＳｂＢｒ３进行原子簇反应均能获得意外产物｛［Ｍｏ３（μ３－Ｓ）（μ－Ｓ２）２（ｄｔｐ）３］（μ３－Ｓ）（η＾３－Ｓ２）［Ｍｏ２（μ３－Ｓ）（μ－Ｓ）３（μ－ＯＡｃ）（ｄｔｐ）２］｝六核钼簇。

Quasi—aromaticity in Cluster Chemistry Ⅱ.Localized Molecular Orbital

The energy-localized CNDO/2 molecular orbitals have been calculated for the cluster anions of [Co_6 (CO)_(14)]￣(4-) and [Ni_2Co_4 (CO)_(14)]￣(2-)in order to get a deeper insight into the nature of their skeletal bonding. The bonding characteristics of these hexanuclear carbonyl cobaltates are described from a localization bonding viewpoint. There are two typical M-CO bondings, one of which is formed by electron donation from the terminal and capping carbonyl ligands into the vacant hybrid orbitals on the metal atoms , leading to formation ofσ(C_t→Co) and σ(C_b→{Co_3})bonds. The other typical M-CO bonding is back donation of the lone d-electron pairs on the metal atoms into the carbonyl ligands, forming π(Co→C_t) bonds, σ(Co→{C_(b2)}) bonds and π(Co→{C_(b4)} ) bonds. It is found that there are no direct metalmetal bondings in the skeletons of these two cluster anions.The delocalization situation of the skeletal bonding electrons is briefly discussed.

同多钒酸盐[Zn(phen)_2]_2[V_4O_(12)]·3H_2O的水热合成及晶体结构

利用水热合成方法合成了组成为[Zn(phen)2 ]2 [V4O12 ]·3H2O的化合物,它以V4O4-12 和Zn(phen)2+2 形成的六核簇为结构单元且通过氢键作用而形成超分子体系. 晶体结构数据如下:三斜晶系,空间群Pī,a= 1. 029(2)nm, b= 1. 111(2)nm, c= 1. 327(3)nm,α= 105. 36 ( 3 )°,β= 92. 01 ( 3 )°,γ= 108. 79 ( 3 )°, V=1. 372 ( 5 )nm3, Z= 1, Dcalc= 1. 575g·cm-3,F(000) = 2 577, R1 = 0. 078 0, wR2 = 0. 175 4.