Hydrothermal Syntheses and Characterizations of Two One-dimensional Molybdenum 1,4-Butylenediphosphonates

1 INTRODUCTION Interest in metal phosphonate chemistry has in- creased in recent years, not only because of their rich structural chemistry[1～3] but also owing to their potential applications in catalysis, absorption and intercalation reaction[4～6]. The introduction of a se- cond metal-ligand component as a charge-compen- sating unit and structure-directing component into polyoxomolybdenum/oxovanadium organodi-phos- phonates has provided us a powerful method to syn- thesize this family o…     

Synthesis,Crystal Structure and MMCT Property of a New Mixed-valence Cyanide-bridged Binuclear Complex

A new mixed-valence cyanide-bridged complex, Br3Fe(μ-NC)RuBr(dppm)2(dppm = bis(diphenylphosphino)methane), was obtained through the reaction between trans-(dppm)2ClRuCN and FeBr3. Its crystal structure was characterized. Electronic absorption spectra indicate the existence of metal-to-metal charge transfer(MMCT) and this complex is Class Ⅱ mixed valence complexes according to the classification of Robin and Day. Magnetic analysis shows it is paramagnetic.     

Synthesis and Crystal Structure of a Heterometallic Trinuclear Ni/Ag/S Compound

A new tri-nuclear mixed metal thiolate complex [Ag(PPh3)2]2[Ni(edtO2)2] 1 has been synthesized and structurally characterized by single-crystal diffraction.The molecule has a crystallographic inversion centre occupied in the central Ni(II) atom and the two silver(I) atoms are related by the inversion centre.The unique structural feature is that one of thiolates of each edt ligand has been oxidized to sulfinate from the precursor [Ni(edt)2]2-to the neutral linear trinuclear complex.The crystal structure belongs to the monoclinic system,space group P21/n with a = 13.581(11),b = 12.239(9),c = 22.316(17) ,β = 103.08(2)o,V = 3613(5) 3,Z = 2,Mr = 1571.87,Dc = 1.445 g/cm3,μ = 1.046 mm-1,F(000) = 1604,T = 293(2) K,the final R = 0.0652 and wR = 0.1499 for 6776 observed reflections with I > 2σ(I).     

Mo－Cu－S原子簇化合物［Mo_2Cu_6S_6（SCMe_3）_2（O）_

基于标题簇合物的快原子质谱研究，提出该二簇合物在质谱过程中的可能断裂途径及其簇骼转换的相关性。     

[(CH_3)_4N]_2Na[Mo_2O(S_2)_3S_5]·H_2O的合成和晶体结构

标题晶体属斜方晶系,空间群Pbn2_1,a=9.086(2),b=13.439(3),c=22.858(11),V=2791,Z=4,Dc=1.927g/cm~3。在CAD—4衍射仪上收集强度数据,采用直接法和Fourier技术解出结构,并用全矩降最小二乘法修正。对于1180个独立衍射最终偏离因子0.067。结构中的阴离子与其同系物[(CH_3)_4-N]_2K(Mo_2O(S_2)_3(NO)_2]·H_2O中的阴离子配位情况相似。只是结构中的Mo—S与Mo—O键长有差异。这种差异在两者的红外光谱上有着相应的表现。     

Co-crystallization of Resorcin[4]arene Tetracarboxylic Acid with Triethylamine: Synthesis and Crystal Structure

Treatment of resorcin[4]arene tetracarboxylic acid 1 with triethylamine in the presence of Co(CH3COO)2·4H2O and 4,4'-bipyridine gave a co-crystallization 14-·4Et3NH+(C32H20O164-·4Et3NH+,Mr=1069.27) from ethanol and water.The compound was structurally determined by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P21/n,with a=8.1763(18),b=12.913(3),c=28.724(7) ,β=97.574(4)o,V=3006.3(12) 3,Z=2,Dc=1.181 g/cm3,F(000)=1152,Rint=0.0275,T=293(2) K,μ=0.086 mm-1,the final R=0.0634 and wR=0.1752 for 5082 observed reflections with Ⅰ 2σ(Ⅰ).The co-crystallization is very stable at room temperature.Possibly,a network of N-H···O(=C) plays an important role in the structure.Meanwhile,the compound emits a weak cyan luminescence with peak maximum band at 458 nm.     

Influence of Ligand with Fine Difference at Donor Site on MMCT Property in Binuclear Mixed Valence Complexes

To investigate how the electronic effect of ligand at donor site influences electronic communication or metal-to-metal charge transfer(MMCT)properties in similar mixed-valence(MV)complexes,a series of binuclear organometallic complexes,MeCp(dppe)RuCNFeCl₃(1),MeCp(PPh₃)₂RuCNFeCl₃(2),Cp^*(dppe)FeCNFeCl₃(3),Cp^*(dppe)RuCNFeCl₃(4)and Cp^*(PPh₃)₂RuCNFeCl₃(5),have been synthesized and characterized.The electronic absorptions of these complexes show the presence of MMCT properties between RuⅡ or FeⅡ and FeⅢ ions,strongly supported by the theoretical calculations.With increasing electron-donating ability of ligands(PPh3>dppe,Cp^*>MeCp)at donor site,the MMCT absorption bands are red-shifted,which expresses in the sequence of absorption bands with 1(500 nm),4(536 nm),2(542 nm),5(580 nm)from high-energy to low-energy.Meanwhile,the MMCT absorption energy of 4(536 nm)is larger than that of 3(760 nm)due to the stronger electron-donating ability of FeⅡ than RuⅡ.Furthermore,these complexes belong to the Class Ⅱ systems according to the Robin and Day’s classification.     

Syntheses and Crystal Structures of a Series of Coordination Complexes Derived from the Fluorescein Ligand

Solvothermal reaction of lanthanide(Ⅲ) salts with fluorescein (2-(6-hydroxy3-oxo-3H-xanthen-9-yl)benzoic acid) led to a series of new coordination polymers {[Ln(C 20 H 11 O 5)(C 20 H 10 O 5)(H 2 O)]·DMF} n (Ln=Er,Eu,Gd,Tb,Tm,Yb).The PXRD patterns of the complexes indicate they are isomorphous.The structure of complex {[Er(C 20 H 11 O 5)(C 20 H 10 O 5)(H 2 O)]·DMF} n has been determined by single-crystal X-ray diffraction,revealing a 2D framework in which DMF molecules were filled between the layers.The crystal structure belongs to the triclinic system,space group P1,with a=12.107(4),b=12.232(4),c=13.273(4),α=68.005(7),β=88.024(11),γ=77.451(8)°,V=1776.7(9) 3,Z=2,D c=1.720 g/cm 3,μ=2.434 mm-1,F(000)=918,R int=0.0584,T=293(2) K,the final R=0.0621 and wR=0.1501.     

Dinuclear Copper（Ⅱ） Complex with a New Polycarboxylate Ligand：Syntheses,Characterization and Crystal Structure

A dinuclear copper(Ⅱ) complex,[Cu2(HL)2(H2O)6] 1(H3L = 2,4,6-tri(3-carboxy-phenylthio)-1,3,5-triazine),was synthesized hydrothermally and characterized by single-crystal X-ray diffraction,IR and thermal analysis.Single-crystal X-ray diffraction reveals that complex 1 is a dinuclear copper(Ⅱ) complex,which is further extended to a 3D network by weak interactions such as O…H-O hydrogen bonds and noncovalent S...S interactions.The crystal of compound 1 belongs to monoclinic,space group C2/c,with a = 50.15(2),b = 6.789(3),c =15.667(8) ,β = 90.588(9)o,V = 5334(4) 3,Z = 4,C48H38Cu2N6O18S6,Mr = 1306.28,Dc = 1.627 g/cm3,F(000) = 2664,Rint = 0.0631,T = 293(2) K,μ = 1.112 mm-1,the final R = 0.0661 and wR = 0.1850 for 3782 observed reflections with I > 2σ(I).