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.     

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.     

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).     

链状三核异金属簇阴离子［Cl_2FeS_2M＇（PPh_3）_2］~－（M＝Mo

在５５０～９０ｃｍ~（－１）波数范围内，测量簇阴离子［Ｃｌ_２ＦｅＳ_２ＭＳ_２Ｍ′（ＰＰｈ_３）_２］~－（Ｍ＝Ｍｏ，Ｍ′＝Ａｇ；Ｍ＝Ｗ，Ｍ′＝Ｃｕ，Ａｇ）的付里叶变换红外光谱，并对标题簇阴离子［Ｃｌ_２ＦｅＳ_２ＷＳ_２Ｃｕ（ＰＰｈ_３）_２］~－，［Ｃｌ_２ＦｅＳ_２ＭｏＳ_２Ａｇ（ＰＰｈ_３）_２］~－和［Ｃｌ_２ＦｅＳ_２ＷＳ_２Ａｇ（ＰＰｈ_３）_２］~－骨架的振动光谱给予经验指认。同时采用＂诱导自洽方法计算振动力常数＂程序，对簇骨架［Ｃｌ_２ＦｅＳ_２ＭＳ_２Ｍ~′Ｐ_２］进行简正坐标分析。振动频率的计算值与观测值符合良好，两者平均偏差小于１．０％，计算结果支持了振动谱带的归属并表明计算力常数的合理性。文中还讨论了主要价键振动频率的变化规律。     

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).     

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.     

A 2D Layered Thiostannate:Synthesis and Crystal Structure of [tmdpH_2]Sn_3S_7

A new thiostannate,[tmdpH2]Sn3S7 1(tmdp = 4,4'-trimethylenedipiperidine),has been synthesized under solvothermal conditions and characterized by elemental analysis,IR spectroscopy,and single-crystal X-ray diffraction analysis.In 1,the Sn3S4 secondary incomplete cubane-like building units are bridged by μ2-S atoms to form Sn12S12 rings which are then joined parallelly to the [001] plane,giving the final 2D(Sn3S72-)n layer of(6,3) network.The layers are stacked along the c axis so that 24-membered ring channels are generated,in which the organic cations are accommodated.The compound crystallizes in monoclinic,space group C2/c,with a=23.052(3),b=13.4039(12),c=18.412(2),β=120.112(4)°,V=4921.3(9)3,C13H28N2S7Sn3,Mr=792.86,Z=8,Dc=2.140 g/cm3,F(000)=3056,μ=3.619 mm-1,the final R=0.0488 and wR=0.1125 for 4607 observed reflections with I2σ(I).     

Two New Coordination Polymers Assembled with a Functionalized Ligand：Syntheses and Crystal Structures

Two new transition-metal organic coordination polymers [M(mna)2](M = Cd(1),Zn(2);mna = 2-mercaptonicotinic anion) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction along with IR and elemental analyses.Compound 1 is generally a one-dimensional linear structure bridged through the sulfur donor of mna ligand,while 2 is a one-dimensional zigzag chain ligated via the oxygen donor of mna ligand.These compounds further result in three-dimensional structures via intermolecular π...π stacking interactions and/or hydrogen bonding interactions.The two compounds were structurally determined by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic space group P21/c with a = 3.730(3),b = 13.973(12),c = 12.380(11) ,β = 97.953(18)°,V = 639.0(10) 3,Z = 2,CdC12H8O4N2S2,Mr = 420.72,Dc = 2.187 g/cm3,F(000) = 412,Rint = 0.0252,T = 293(2) K,μ = 2.052 mm?1,the final R = 0.0269 and wR = 0.0586 for 1377 observed reflections with I > 2σ(I).Complex 2 belongs to monoclinic space group P21/c with a = 13.376(2),b = 12.8429(14),c = 7.4856(10) ,β = 96.190(10)°,V = 1278.5(3) 3,Z = 4,ZnC12H8O4N2S2,Mr = 373.69,Dc = 1.941 g/cm3,F(000) = 752,Rint = 0.0414,T = 293(2) K,μ = 2.264 mm?1,the final R = 0.0418 and wR = 0.0966 for 2396 observed reflections with I > 2σ(I).     

Three New Zn(Ⅱ)/Cd(Ⅱ) Coordination Polymers Constructed with 2-Mercaptonicotinic Acid and 1,2-Di(4-pyridyl)ethylene: Syntheses and Structure Analysis

Three new Zn(Ⅱ)/Cd(Ⅱ) coordination polymers based on 2-mercaptonicotinic acid (H2mna) with 1,2-di(4-pyridyl)ethylene (dpe) introduced as a bridging ligand have been synthesized via hydrothermal method and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. As reported in this paper, [Zn2(dpe)0.5(mna)2] (1) can be classified as a two-dimensional layer structure in which the 1D chain composed of Zn(Ⅱ) and mna ligands is bridged by dpe ligands, while the complex named [Zn4(dpe)4(mna)4] (2) is a tetra-nuclear cluster compound. These two compounds are further extended to three-dimensional structures by hydrogen bonds along with C-H…π and π…π interactions. Compound 3 with general formular [Cd2(dpe)0.5(mna)2]·H2O belongs to a three-dimensional porous structure in which the 2D metal layers formed by the coordination of Cd(Ⅱ) and mna ligands are connected with the bridging of dpe ligands.