The heteroleptic dmit complex Et 4N 2 Ni 2(C 2S 4)(C 3S 5) 2 has been prepared by the reaction of NiCl 2·H 2O with Na 2dmit, NaSC 2H 4OH in the MeOH solution. The compound has been characteriz...The heteroleptic dmit complex Et 4N 2 Ni 2(C 2S 4)(C 3S 5) 2 has been prepared by the reaction of NiCl 2·H 2O with Na 2dmit, NaSC 2H 4OH in the MeOH solution. The compound has been characterized by X ray diffraction study, IR and UV Vis spectroscopy. Crystallographic data : space group: P2 1/n, a=11.843(2), b=11 079(1), c = 15.404(1) , β=110.33(1)°, V = 1895.1 3, Z=2, D c =1.62 g/cm 3 , μ =17.6 cm -1 , F (000)=956, R=0.052, R w =0.061. In the structure of the title complex, the tto (tto=tetrathioxalato) ligand in bridging form is chelated to two nickel atoms and dmit (dmit=1,3 dithiole 2 thione 4,5 dithiolate) ligands coordinated to nickel atoms.展开更多
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 ...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.展开更多
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 dif...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）.展开更多
The creation of a porous magnet is a long-sought academic goal since magnetism and porosity are hostile to one another. While long-range magnetic ordering needs spin carriers of short separation through short bridges,...The creation of a porous magnet is a long-sought academic goal since magnetism and porosity are hostile to one another. While long-range magnetic ordering needs spin carriers of short separation through short bridges, porosity relies on the use of extended connecting ligands. Here, we will give a survey of the cluster-based magnetic porous coordination polymers, i.e., 0-D MPCPs, according to their functional subunits： （1） nanoporous spin crossover materials with single metal nodes; （2） metal-radical approach with rigid organic radical ligands and single metal nodes; （C） PCPs with rigid organic ligands and metal oligomer nodes; （D） PCPs with metal complex linkers and polymetal cluster nodes; （E） PCPs with organo-polymetal cluster linkers and single metal nodes. The assembly from clusters can provide a reasonable route to resolve the hostility between magnetism and porosity. This assembly’s merits are obvious： the pore benefits from the big cluster according to ＂Scale Chemistry＂, and the functional framework inherits interesting physical properties from the clusters with a large ground spin S.展开更多
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 ana...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）.展开更多
A new tetranuclear cyanide-bridged complex [PPh4]2[NiⅡ（CN）4CuⅠ（PPh3）2]2·2CH3OH （[PPh4]＋ = tetraphenylphosphine cation, PPh3 = triphenylphosphine） 1 has been synthesized and characterized by IR spectrosco...A new tetranuclear cyanide-bridged complex [PPh4]2[NiⅡ（CN）4CuⅠ（PPh3）2]2·2CH3OH （[PPh4]＋ = tetraphenylphosphine cation, PPh3 = triphenylphosphine） 1 has been synthesized and characterized by IR spectroscopy, elemental analysis, electronic absorption spectra and single-crystal X-ray diffraction. This complex crystallizes in triclinic, space group Pí with a = 10.910（5）, b = 15.777（7）, c = 18.275（8）, α = 68.752（12）, β = 79.776（13）, γ = 81.400（14）°, NiCuC65H50N4OP3, Mr = 1122.25, V = 2873（2）3 , Z = 2, Dc = 1.293 g/cm3, F（000） = 1156, μ = 0.826 mm-1, the final R = 0.0755 and wR = 0.2155 for 7324 observed reflections （I 2σ（I））. The title compound exhibits a discrete square tetranuclear structure and a cubic order NLO property.展开更多
Two manganese complexes, [Mn3（2-cba）6（phen）2] 1 （2-cba = 2-cyanobenzoic acid, phe11 = 1,10-phenanthroline） and [MnE（4-fbaO）E（phen）4]（PF6）E.EHEO 2 （4-fbao = 4-formylbenzoic acid oxime）, have been synthesi...Two manganese complexes, [Mn3（2-cba）6（phen）2] 1 （2-cba = 2-cyanobenzoic acid, phe11 = 1,10-phenanthroline） and [MnE（4-fbaO）E（phen）4]（PF6）E.EHEO 2 （4-fbao = 4-formylbenzoic acid oxime）, have been synthesized by the reaction of 2-formylbenzoic acid oxime （2-fbao, HELl） or 4-formylbenzoic acid oxime （4-fbao, HELE） with phen and manganese acetate in ethanol or methanol solution. A translation from the oximino （-CHN=OH） of HELl to cyano （-C-N） was found in the formation of complex 1 at room temperature. The complexes were structurally determined by single-crystal X-ray diffraction. The crystal of compound I belongs to monoclinic, space group C2/c, with a = 17.983（6）, b = 23.364（7）, c =14.589（5） A, β = 92.401（5）° V = 6124（3） A^3, Z = 4, C72H40Mn3N10O12, Mr= 1401.96, Dc = 1.521 g/cm^3, F（000） = 2852.0, Rint = 0.0372, T= 293（2） K,μ = 0.686 mm^-1, the final R = 0.0644 and wR = 0.1813 for 5803 observed reflections with I 〉 2δ（I）. The crystal of compound 2 is of monoclinic system, space group P21/n, with a = 13.050（4）, b = 20.577（5）, c = 13.323（4）A,β = 113.578（3）°, V = 3227.2（14）A3, Z = 2, C64H48F12Mn2N10O8P2, Mr = 1484.94, Dc = 1.528 g/cm^3, F（000） = 1508.0, Rint= 0.0295, T= 293（2） K,μ = 0.539 mm^-1, the final R = 0.0629 and wR = 0.1789 for 5298 observed reflections with I 〉 2σ（I）. Compounds 1 and 2 are linear trinuclear and dinuclear manganese complexes respectively, which are both bridged by carboxylate groups of the ligands.展开更多
Two one-dimensional chain-like cyanide-bridged compounds, [Fe（Phen）2（CN）2Ni（Cyclam）]（ClO4）2·DMF-2H2O 1 （Cyclam = 1,4,8,11-tetraaza-cyclotetradecane, Phen = 1,10-phenanthroline, and DMF = N,N-dimethylform...Two one-dimensional chain-like cyanide-bridged compounds, [Fe（Phen）2（CN）2Ni（Cyclam）]（ClO4）2·DMF-2H2O 1 （Cyclam = 1,4,8,11-tetraaza-cyclotetradecane, Phen = 1,10-phenanthroline, and DMF = N,N-dimethylformamide） and [Fe（Phen）2（CN）2Zn（Cyclam）]（PF6）2·CH3CN 2, were prepared by the reaction of [Fe（Phen）2（CN）2]·2H2O with M（Cyclam）^2＋ （M = Ni, Zn）. In complexes 1 and 2, the metal atoms are connected alternatively with CN groups. X-ray structure and IR analyses for 1 and 2 were performed. Structure analysis revealed that both complexes are centrosymmetric and the geometry around each metal atom is an octahedron. The two complexes crystallize in triclinic with space group of P^1-. For 1, a = 10.439（4）, b = 14.976（7）, c = 15.914（8）A,α = 83.168（15）, β = 74.338（15）, γ = 78.023（15）°, V = 2338.3（18）A^3, Z = 2, Mr = 1035.37, Dc = 1.471 g/cm^3, F（000） = 1076,μ = 0.895 mm^-1, the final R = 0.0616 and wR = 0.1414 for 5849 observed reflections （1 〉 2σ（I））. For 2, a = 9.656（6）, b = 15.404（9）, c = 15.822（10）A, α = 78.68（2）, β= 78.917（19）, γ = 77.15（2）°, V = 2223（2）A^3, Z = 2, Mr = 1064.87, Dc = 1.587 g/cm^3, F（000） = 1078,μ = 1.032 mm^-1, the final R = 0.0672 and wR = 0.1595 for 6819 observed reflections （I 〉 2σ（I））.展开更多
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 diffracti...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（Sn3S7^2-）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）A,β=120.112（4）°,V=4921.3（9）A^3,C13H28N2S7Sn3,Mr=792.86,Z=8,Dc=2.140 g/cm^3,F（000）=3056,μ=3.619 mm^-1,the final R=0.0488 and wR=0.1125 for 4607 observed reflections with I〉2σ（I）.展开更多
A new mixed-valence cyanide-bridged complex, Br3Fe（p-NC）RuBr（dppm）2 （dppm = bis（diphenylphosphino）methane）, was obtained through the reaction between trans-（dppm）2C1- RuCN and FeBr3. Its crystal structure wa...A new mixed-valence cyanide-bridged complex, Br3Fe（p-NC）RuBr（dppm）2 （dppm = bis（diphenylphosphino）methane）, was obtained through the reaction between trans-（dppm）2C1- RuCN 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.展开更多
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 occu...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）.展开更多
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）]·...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.展开更多
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...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.展开更多
Two cyanide bridged trinuclear compounds [Fe（bpy）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·DMF 1 and [Fe（Phen）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·2CH3CN·4H2O 2 （Bpy = 2,2＇- bipyridine, Phen = 1,...Two cyanide bridged trinuclear compounds [Fe（bpy）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·DMF 1 and [Fe（Phen）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·2CH3CN·4H2O 2 （Bpy = 2,2＇- bipyridine, Phen = 1,10-phenanthroline, Cyclam = 1,4,8,11-tetraaza-cyclotetradecane, and DMF = N,N-dimethylformamide） have been synthesized by using mononuclear [Fe（Phen）2（CN）2]·2H2O and [Fe（bpy）2（CN）2]·3H2O as precursors. These two complexes crystallize in monoclinic space groups P21/c and C2/c, respectively. For 1, a = 25.164（2）, b = 12.0405（11）, c = 20.4433（15） A, β = 91.948（3）°, V = 6190.5（9） A^3, Z = 4, Mr = 1418.90, Dc = 1.522 g/cm^3, F（000） = 2936, μ = 1.161 mm^-1, the final R = 0.0722 and wR = 0.2011 for 10779 observed reflections （I 〉 2σ（I））. For 2, a = 43.5945（0）, b = 11.8447（0）, c = 29.5637（2）A, β = 120.430（11）o, V = 13162.76（9） A^3, Z = 8, Mr = 1518.48, Dc = 1.533 g/cm^3, F（000） = 6288, μ = 1.101 mm^-1, the final R = 0.0711 and wR = 0.1783 for 11262 observed reflections （I 〉 2σ（I））.展开更多
A neutral dinuclear compound Cu2[（O=PPh2）2N]2（μ-O2PPh2）2 has been unexpectedly prepared from the reaction of [Cu2（dppa）2（MeCN）4]（ClO4）2 （dppa = bis（diphenylphosphino）- amine） and Sn（edt）2（edt = ethan...A neutral dinuclear compound Cu2[（O=PPh2）2N]2（μ-O2PPh2）2 has been unexpectedly prepared from the reaction of [Cu2（dppa）2（MeCN）4]（ClO4）2 （dppa = bis（diphenylphosphino）- amine） and Sn（edt）2（edt = ethane-1,2-dithiolate） in dichloromethane in air. ESR spectrum shows that the original Cu^＋ ion has been oxidized. The crystal structure determined by an X-ray single diffractometer displays that the concurrence of the redox and hydrolysis of the origin ligand dppa is taken with the formation of two new ligands. The complex crystallizes in triclinic, space group P1^- with a = 9.4269（13）, b = 10.7522（13）, c = 16.787（2）A^°, α= 92.042（5）, β= 104.591（7）, γ = 96.167（6）°, V= 1633.6（4） A^°3, C72H60 Cu2N2O8P6, Mr = 1394.12, Z = 1, D,. = 1.419 g/cm^3, F（000） = 718,μ = 0.856 mm^-1, the final R = 0.0530 and wR = 0.1096 for 4210 observed reflections with I 〉 2σ（I）.展开更多
A chiral salency complex,[Mn（Salency）（H2O）2]（PF6）·2H2O 1（Salency =（R,R）-N,N＇-bis（salicylidene）-1,2-cyclohexanediamine）,has been prepared by the reaction of Mn（CH3COO）3·2H2O with Salency and NH...A chiral salency complex,[Mn（Salency）（H2O）2]（PF6）·2H2O 1（Salency =（R,R）-N,N＇-bis（salicylidene）-1,2-cyclohexanediamine）,has been prepared by the reaction of Mn（CH3COO）3·2H2O with Salency and NH4PF6,and was established by X-ray diffraction techniques.The complex crystallizes in triclinic,space group P1 with a=9.299（8）,b=10.012（8）,c=13.461（11）,α=92.037（15）,β=92.974（12）,γ=93.530（18）°,V=1248.3（18）3,C20H28F6MnN2O6P,Mr = 592.35,Z=2,Dc=1.038 g/cm3,F（000）=608,μ=0.676 mm–1,the final R=0.0651 and wR=0.1880 for 5260 observed reflections with I 2σ（I）.展开更多
A new metal-organic framework, {[Cd（DPA）（OBA）]＇（HzO）}n （1, DPA = 4,4＂-dipyri- dylamine, H2OBA = 4,4＂-oxybisbenzoic acid）, has been synthesized and characterized by elemental analysis, IR and single-crystal ...A new metal-organic framework, {[Cd（DPA）（OBA）]＇（HzO）}n （1, DPA = 4,4＂-dipyri- dylamine, H2OBA = 4,4＂-oxybisbenzoic acid）, has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Single-crystal X-ray analysis shows that it is a 3-D framework. Complex 1 crystallizes in monoclinic, space group C2/c with a = 21.699（7）, b = 12.192（4）, c = 17.566（5） A, β = 105.254（5）°, V = 4483.43 A3, Z = 8, Dc = 1.653 g/cm3, p = 1.021 mm^-1], F（000） = 2240, the final R = 0.0307, wR = 0.0867 （I 〉 2σ（I））. Complex I exhibits a rare three-dimensional highly 8-connected LOMFOI topology with a point symbol of {424＂64}. Thermogravimetric analysis shows that the decomposition temperature of the host framework of the complex is above 400 ℃.展开更多
Two new metal-organic frameworks, {[Cd2CI（HL）（H20）2＂0.5H20]}n （1） and {[Cd2L（H20）2]＇H20}n （2）, have been hydrothermally synthesized with designed ligand H4L （HaL = 1,3,5-triazine-2-iminodiacetic acid-4,6-...Two new metal-organic frameworks, {[Cd2CI（HL）（H20）2＂0.5H20]}n （1） and {[Cd2L（H20）2]＇H20}n （2）, have been hydrothermally synthesized with designed ligand H4L （HaL = 1,3,5-triazine-2-iminodiacetic acid-4,6-biglycine） under the same condition except for different pH values. Single-crystal X-ray determination shows that they are 3-D frameworks. Complex 1 crystallizes in monoclinic, space group P21/n. Complex 2 crystallizes in triclinic, space group Pi. The photoluminescence properties of those two complexes have been investigated in solid state. Complexes 2 exhibited remarkable blue luminescence emissions with high quantum yield of 40.3% On the other hand, complexes 1 featured weak quantum yields of 13.7%.展开更多
文摘The heteroleptic dmit complex Et 4N 2 Ni 2(C 2S 4)(C 3S 5) 2 has been prepared by the reaction of NiCl 2·H 2O with Na 2dmit, NaSC 2H 4OH in the MeOH solution. The compound has been characterized by X ray diffraction study, IR and UV Vis spectroscopy. Crystallographic data : space group: P2 1/n, a=11.843(2), b=11 079(1), c = 15.404(1) , β=110.33(1)°, V = 1895.1 3, Z=2, D c =1.62 g/cm 3 , μ =17.6 cm -1 , F (000)=956, R=0.052, R w =0.061. In the structure of the title complex, the tto (tto=tetrathioxalato) ligand in bridging form is chelated to two nickel atoms and dmit (dmit=1,3 dithiole 2 thione 4,5 dithiolate) ligands coordinated to nickel atoms.
基金supported by grants from the 973 Program(2012CB821702)the National Natural Science Foundation of China(21073192,21173223 and 21173220)the Science Foundation of CAS(KJCX2-YW-H20)and of Fujian Province(2009HZ0006-1)
文摘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.
基金supported by grants from the 973 Program (2007CB815301)the National Natural Science Foundation of China (21073192, 20733003 and 20871114)+1 种基金the Science Foundation of CAS (KJCX2-YW-H20)Fujian Province (2009HZ0006-1,2006L2005)
文摘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）.
基金supported by the State Key Laboratory of Structural Chemistry, NNSFC (20733003)Chinese Academy of Sciences (KJCX2-YW-M05)+1 种基金973 Program (2007CB815301, 2006CB932900)the NSF of Fujian Province (2006L2005, 2006J0014)
文摘The creation of a porous magnet is a long-sought academic goal since magnetism and porosity are hostile to one another. While long-range magnetic ordering needs spin carriers of short separation through short bridges, porosity relies on the use of extended connecting ligands. Here, we will give a survey of the cluster-based magnetic porous coordination polymers, i.e., 0-D MPCPs, according to their functional subunits： （1） nanoporous spin crossover materials with single metal nodes; （2） metal-radical approach with rigid organic radical ligands and single metal nodes; （C） PCPs with rigid organic ligands and metal oligomer nodes; （D） PCPs with metal complex linkers and polymetal cluster nodes; （E） PCPs with organo-polymetal cluster linkers and single metal nodes. The assembly from clusters can provide a reasonable route to resolve the hostility between magnetism and porosity. This assembly’s merits are obvious： the pore benefits from the big cluster according to ＂Scale Chemistry＂, and the functional framework inherits interesting physical properties from the clusters with a large ground spin S.
基金supported by grants from the 973 Program (2007CB815301)the National Science Foundation of China (21073192,20733003, 20871114 and 20801055)+1 种基金the Science Foundation of CAS (KJCX2-YW-H20)Fujian Province (2009HZ0006-1,2006L2005)
文摘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）.
基金supported by grants from the 973 Program(2012CB821700)the National Natural Science Foundation of China(21073192,20871114 and 21173223)the Science Foundation of CAS(KJCX2-YW-H20)and of Fujian Province(2009HZ0006-1)
文摘A new tetranuclear cyanide-bridged complex [PPh4]2[NiⅡ（CN）4CuⅠ（PPh3）2]2·2CH3OH （[PPh4]＋ = tetraphenylphosphine cation, PPh3 = triphenylphosphine） 1 has been synthesized and characterized by IR spectroscopy, elemental analysis, electronic absorption spectra and single-crystal X-ray diffraction. This complex crystallizes in triclinic, space group Pí with a = 10.910（5）, b = 15.777（7）, c = 18.275（8）, α = 68.752（12）, β = 79.776（13）, γ = 81.400（14）°, NiCuC65H50N4OP3, Mr = 1122.25, V = 2873（2）3 , Z = 2, Dc = 1.293 g/cm3, F（000） = 1156, μ = 0.826 mm-1, the final R = 0.0755 and wR = 0.2155 for 7324 observed reflections （I 2σ（I））. The title compound exhibits a discrete square tetranuclear structure and a cubic order NLO property.
基金grants from the 973 Program (2007CB815301 and 2006CB932900)the National Natural Science Foundation of China (20733003 and 20673118)+1 种基金the Science Foundation of CAS (KJCX2-YW-M05)Fujian Province (2006F3132 and 2005HZ01-1)
文摘Two manganese complexes, [Mn3（2-cba）6（phen）2] 1 （2-cba = 2-cyanobenzoic acid, phe11 = 1,10-phenanthroline） and [MnE（4-fbaO）E（phen）4]（PF6）E.EHEO 2 （4-fbao = 4-formylbenzoic acid oxime）, have been synthesized by the reaction of 2-formylbenzoic acid oxime （2-fbao, HELl） or 4-formylbenzoic acid oxime （4-fbao, HELE） with phen and manganese acetate in ethanol or methanol solution. A translation from the oximino （-CHN=OH） of HELl to cyano （-C-N） was found in the formation of complex 1 at room temperature. The complexes were structurally determined by single-crystal X-ray diffraction. The crystal of compound I belongs to monoclinic, space group C2/c, with a = 17.983（6）, b = 23.364（7）, c =14.589（5） A, β = 92.401（5）° V = 6124（3） A^3, Z = 4, C72H40Mn3N10O12, Mr= 1401.96, Dc = 1.521 g/cm^3, F（000） = 2852.0, Rint = 0.0372, T= 293（2） K,μ = 0.686 mm^-1, the final R = 0.0644 and wR = 0.1813 for 5803 observed reflections with I 〉 2δ（I）. The crystal of compound 2 is of monoclinic system, space group P21/n, with a = 13.050（4）, b = 20.577（5）, c = 13.323（4）A,β = 113.578（3）°, V = 3227.2（14）A3, Z = 2, C64H48F12Mn2N10O8P2, Mr = 1484.94, Dc = 1.528 g/cm^3, F（000） = 1508.0, Rint= 0.0295, T= 293（2） K,μ = 0.539 mm^-1, the final R = 0.0629 and wR = 0.1789 for 5298 observed reflections with I 〉 2σ（I）. Compounds 1 and 2 are linear trinuclear and dinuclear manganese complexes respectively, which are both bridged by carboxylate groups of the ligands.
基金the grants from 973 Program (2007CB815301 and 2006CB932904)the National Natural Science Foundation of China (20333070 and 20673118)+1 种基金the Science Foundation of CAS (KJCX2-YW-M05)Fujian Province (2006L2005, 2006F3132 and 2007J0171)
文摘Two one-dimensional chain-like cyanide-bridged compounds, [Fe（Phen）2（CN）2Ni（Cyclam）]（ClO4）2·DMF-2H2O 1 （Cyclam = 1,4,8,11-tetraaza-cyclotetradecane, Phen = 1,10-phenanthroline, and DMF = N,N-dimethylformamide） and [Fe（Phen）2（CN）2Zn（Cyclam）]（PF6）2·CH3CN 2, were prepared by the reaction of [Fe（Phen）2（CN）2]·2H2O with M（Cyclam）^2＋ （M = Ni, Zn）. In complexes 1 and 2, the metal atoms are connected alternatively with CN groups. X-ray structure and IR analyses for 1 and 2 were performed. Structure analysis revealed that both complexes are centrosymmetric and the geometry around each metal atom is an octahedron. The two complexes crystallize in triclinic with space group of P^1-. For 1, a = 10.439（4）, b = 14.976（7）, c = 15.914（8）A,α = 83.168（15）, β = 74.338（15）, γ = 78.023（15）°, V = 2338.3（18）A^3, Z = 2, Mr = 1035.37, Dc = 1.471 g/cm^3, F（000） = 1076,μ = 0.895 mm^-1, the final R = 0.0616 and wR = 0.1414 for 5849 observed reflections （1 〉 2σ（I））. For 2, a = 9.656（6）, b = 15.404（9）, c = 15.822（10）A, α = 78.68（2）, β= 78.917（19）, γ = 77.15（2）°, V = 2223（2）A^3, Z = 2, Mr = 1064.87, Dc = 1.587 g/cm^3, F（000） = 1078,μ = 1.032 mm^-1, the final R = 0.0672 and wR = 0.1595 for 6819 observed reflections （I 〉 2σ（I））.
基金supported by the 973 Program (2007CB815301 and 2006CB932904)the National Natural Science Foundation of China (20333070, 20673118, 20871114)+1 种基金the Science Foundation of CAS (KJCX2-YW-M05)Fujian Province (2006L2005, 2006J0014, 2006F3132)
文摘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（Sn3S7^2-）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）A,β=120.112（4）°,V=4921.3（9）A^3,C13H28N2S7Sn3,Mr=792.86,Z=8,Dc=2.140 g/cm^3,F（000）=3056,μ=3.619 mm^-1,the final R=0.0488 and wR=0.1125 for 4607 observed reflections with I〉2σ（I）.
基金supported by the 973 Program(2012CB821702,2014CB845603)the National Natural Science Foundation of China(21233009,21203194 and 21173223)
文摘A new mixed-valence cyanide-bridged complex, Br3Fe（p-NC）RuBr（dppm）2 （dppm = bis（diphenylphosphino）methane）, was obtained through the reaction between trans-（dppm）2C1- RuCN 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.
基金supported by the 973 Program (2007CB815301)the National Natural Science Foundation of China (21073192,20733003 and 20871114)+1 种基金the Science Foundation of CAS (KJCX2-YW-H20)Fujian Province (2009HZ0006-1,2006L2005)
文摘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）.
基金supported by the National Natural Science Foundation of China (20733003,20871114 and 20801055)the Science Foundation of CAS (KJCX2-YW-M05 and KJCX2-YW-H20)of Fujian Province (2009HZ0006-1,2006L2005)
文摘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.
基金Supported by the State Key Laboratory of Structural Chemistry (CAS)the National Natural Science Foundation of China (20733003, 20801055 and 20673118)+1 种基金the Science Foundation of CAS (KJCX2-YW-M05)Fujian Province (2006J0014, 2006F3132 and 2007J0171)
文摘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.
基金Supported by the 973 Program (2007CB815301 and 2006CB932904)the National Natural Science Foundation of China (20333070, 20871114 and 20673118)+1 种基金the Science Foundation of CAS (KJCX2-YW-M05)Fujian Province (2006F3132 and 2007J0171)
文摘Two cyanide bridged trinuclear compounds [Fe（bpy）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·DMF 1 and [Fe（Phen）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·2CH3CN·4H2O 2 （Bpy = 2,2＇- bipyridine, Phen = 1,10-phenanthroline, Cyclam = 1,4,8,11-tetraaza-cyclotetradecane, and DMF = N,N-dimethylformamide） have been synthesized by using mononuclear [Fe（Phen）2（CN）2]·2H2O and [Fe（bpy）2（CN）2]·3H2O as precursors. These two complexes crystallize in monoclinic space groups P21/c and C2/c, respectively. For 1, a = 25.164（2）, b = 12.0405（11）, c = 20.4433（15） A, β = 91.948（3）°, V = 6190.5（9） A^3, Z = 4, Mr = 1418.90, Dc = 1.522 g/cm^3, F（000） = 2936, μ = 1.161 mm^-1, the final R = 0.0722 and wR = 0.2011 for 10779 observed reflections （I 〉 2σ（I））. For 2, a = 43.5945（0）, b = 11.8447（0）, c = 29.5637（2）A, β = 120.430（11）o, V = 13162.76（9） A^3, Z = 8, Mr = 1518.48, Dc = 1.533 g/cm^3, F（000） = 6288, μ = 1.101 mm^-1, the final R = 0.0711 and wR = 0.1783 for 11262 observed reflections （I 〉 2σ（I））.
基金This research was supported by the grants from the State Key Laboratory of Structural Chemistry, the National Science and Technology of China (001CB1089), the Chinese Academy of Sciences (CAS), the National Natural Science Foundation of China (20273073, 20333070, 90206040) and the NaturalScience Foundation of CAS and Fujian Province (2004HZ01-1, 2004J041, 2003J042)
文摘A neutral dinuclear compound Cu2[（O=PPh2）2N]2（μ-O2PPh2）2 has been unexpectedly prepared from the reaction of [Cu2（dppa）2（MeCN）4]（ClO4）2 （dppa = bis（diphenylphosphino）- amine） and Sn（edt）2（edt = ethane-1,2-dithiolate） in dichloromethane in air. ESR spectrum shows that the original Cu^＋ ion has been oxidized. The crystal structure determined by an X-ray single diffractometer displays that the concurrence of the redox and hydrolysis of the origin ligand dppa is taken with the formation of two new ligands. The complex crystallizes in triclinic, space group P1^- with a = 9.4269（13）, b = 10.7522（13）, c = 16.787（2）A^°, α= 92.042（5）, β= 104.591（7）, γ = 96.167（6）°, V= 1633.6（4） A^°3, C72H60 Cu2N2O8P6, Mr = 1394.12, Z = 1, D,. = 1.419 g/cm^3, F（000） = 718,μ = 0.856 mm^-1, the final R = 0.0530 and wR = 0.1096 for 4210 observed reflections with I 〉 2σ（I）.
基金Supported by the 973 Program (2007CB815301 and 2006CB932904)the National Natural Science Foundation of China (20333070, 20673118, 20871114)+1 种基金the Science Foundation of CAS (KJCX2-YW-M05)Fujian Province (2006J0014, 2006F3132)
文摘A chiral salency complex,[Mn（Salency）（H2O）2]（PF6）·2H2O 1（Salency =（R,R）-N,N＇-bis（salicylidene）-1,2-cyclohexanediamine）,has been prepared by the reaction of Mn（CH3COO）3·2H2O with Salency and NH4PF6,and was established by X-ray diffraction techniques.The complex crystallizes in triclinic,space group P1 with a=9.299（8）,b=10.012（8）,c=13.461（11）,α=92.037（15）,β=92.974（12）,γ=93.530（18）°,V=1248.3（18）3,C20H28F6MnN2O6P,Mr = 592.35,Z=2,Dc=1.038 g/cm3,F（000）=608,μ=0.676 mm–1,the final R=0.0651 and wR=0.1880 for 5260 observed reflections with I 2σ（I）.
基金supported by the National Ministry of Science and Technology of China(2012CB821702)the National Science Foundation of China(21073192,21203194 and 21233009)the Science Foundation of CAS and Fujian Province for research funding support(KJCX2-YW-H20)
文摘A new metal-organic framework, {[Cd（DPA）（OBA）]＇（HzO）}n （1, DPA = 4,4＂-dipyri- dylamine, H2OBA = 4,4＂-oxybisbenzoic acid）, has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Single-crystal X-ray analysis shows that it is a 3-D framework. Complex 1 crystallizes in monoclinic, space group C2/c with a = 21.699（7）, b = 12.192（4）, c = 17.566（5） A, β = 105.254（5）°, V = 4483.43 A3, Z = 8, Dc = 1.653 g/cm3, p = 1.021 mm^-1], F（000） = 2240, the final R = 0.0307, wR = 0.0867 （I 〉 2σ（I））. Complex I exhibits a rare three-dimensional highly 8-connected LOMFOI topology with a point symbol of {424＂64}. Thermogravimetric analysis shows that the decomposition temperature of the host framework of the complex is above 400 ℃.
基金supported the National Ministry of Science and Technology of China(2012CB821702)the National Science Foundation of China(21073192,21203194 and 21233009)the Science Foundation of CAS and Fujian Province(KJCX2-YW-H20)
文摘Two new metal-organic frameworks, {[Cd2CI（HL）（H20）2＂0.5H20]}n （1） and {[Cd2L（H20）2]＇H20}n （2）, have been hydrothermally synthesized with designed ligand H4L （HaL = 1,3,5-triazine-2-iminodiacetic acid-4,6-biglycine） under the same condition except for different pH values. Single-crystal X-ray determination shows that they are 3-D frameworks. Complex 1 crystallizes in monoclinic, space group P21/n. Complex 2 crystallizes in triclinic, space group Pi. The photoluminescence properties of those two complexes have been investigated in solid state. Complexes 2 exhibited remarkable blue luminescence emissions with high quantum yield of 40.3% On the other hand, complexes 1 featured weak quantum yields of 13.7%.
