＜正＞The study of organic-inorganic hybrid polyoxometalates（POMs）is a very active and expanding area because of ...
Hai-Hui Yu Xiao-Bing Cui Ji-Wen Cui Ji-Qing Xu Tie-Gang Wang. College of Chemistry and State Key Laboratory of Inorganic Synthesis and Preparative Chemistry,Jilin University,Changchun,Jilin,130023,P.R..China.
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））.
Two new supramoleeular polymers [ M （2-NH2 py）2 （ox） ] [ M = Co （1）, Ni （2） ; 2-NH2py = 2-aminopyridine; ox = oxalate ] were hydrothermally synthesized and characterized by elemental analyses, IR and single-crystal X-ray diffraction analyses. The isomorphic compounds 1 and 2 both possess one-dimensional zigzag chain structures, which are composed of [ M （2-NH2 py）2 ]^2＋ units bridged by tetradentate oxalate ligands to form three-dimensional supramolecular network v/a the C-H…O hydrogen bonds and π-π stacking interactions. Compound 1 displays antiferromagnetie interaction.
ZHANG Xiao YI Zhi-hui XUE Ming XU Yan YU Jie-hui YU Xiao-yang XU Ji-qing
＜正＞Recently,the study of polyoxometalates covalently linked by transition metal complex fragments has been an ...
Ji-Wen Cui~(a,b) Xiao-Bing,Cui~a Hai-Hui Yu~a Wei-Jie Duan~a Ji-Qing Xu~(a*) Tie-Gang Wang~a a College of Chemistry and State Key Laboratory of Inorganic Synthesis and Preparative Chemistry,Jilin University,Changchun 130021,China. b College of Chemistry and Pharmacy,Jiamusi University,Jiamusi 154000,China
The hydrothermal reaction of 1,2-dicyanobenzene with NaN3 in the presence of CuC12, 2,2＇-bipyridine and H2O affords a novel dinuclear copper（Ⅱ）-ditetrazolate, [Cu（bpy）- （pdtz）]2 （Hpdtz = 5,5＂-1,2-phenylene-ditetrazole, bpy = 2,2＇-bipyridine）. The pdtz ligand is generated in situ through Sharpless 2＋3 cycloaddition reaction. Its crystal structure was determined by single-crystal X-ray diffraction method. The crystal crystallizes in the monoclinic system, space group P211n with a = 8.2096（16）, b = 18.580（4）, c = 11.838（2） A, β = 103.12（3）°, V = 1758.5（6） A^3, Z = 2, Mr = 863.83, Dc = 1.631 g/cm^3, F（000） = 876 and μ = 1.272 mm^-1. In this novel dinuclear structure, the pdtz ligand adopts a peculiar μ2-η1,η2 coordination mode.
HUANG Xi-He SHENG Tian-Lu XIANG Sheng-Chang FU Rui-Biao HU Sheng-Min LI Ya-Min WU Xin-Tao
A novel copper molybdate with mixed ligands, [{（Cu·phen）e（tp）} {（Cu·phen·H2O）2（tp）} {Mo4O14}（phen = 1,10-phcnanthroline, tp = tercphthalate） 1, has been hydrothermally synthesized and structurally characterized. The crystal belongs to monoclinic system, space group P2l/c with a = 13.1711（7）, b = 19.6132（10）, c= 13.6910（7） A, β = 117.6870（10）°, V= 3131.8（3） A^3, Z= 2, C64H44Cu4MoaN8O24, Mr= 1946.99, D, = 2.065 g/cm^3, F（000） = 1920,μ（MoKa） = 2.198 mm ^1, R = 0.0810 and wR = 0.2012 for 4233 observed reflections （I 〉 2σ（I））. The structural analysis indicates that the title compound contains a discrete tetramolybdate cluster decorated with copper colnplcx fragments and tp ligands bridging the clusters into a wave-like layer. The hydrogen bonding between adjacent layers further extends the COlnpound into a 3-D framework.
The hydrothermal reaction of CuBr2 and CuBr with phen·H2O （phen= 1,10-phenanthroline） in a molar ratio of 1：1：1.5 gave birth to the first copper-halo cationic cluster [Cu2^Ⅱ Cu2^Br4 （phen）4 ] ^2＋（1） with tetranuclear anionic cluster [Cu4Br6]^2-. Changing the precursors or their molar ratios, two mononuclear complexes [Cu（phen）2Br]Br·H2O （2） and [Ni（phen）3][CuCl2]2 （3） as well as two unusual copper-halo chains found in polymers [Cu2Br2（phen）]∞ （4） and [Cu^ⅡCu3^ⅠBr2Ⅰ3 （phen）2 ]∞ （5） were obtained. The （Cu2Br2）∞ chain of 4 looks like a linearar ray of hexagons based on fused Cu3Br3 units, and the linear （Cu3Ⅰ3Br^-）∞ chain of 5 is an alternate combination of the rhombic Cu2I2 cores and the Cu4I4Br2^2- units. In addition, the hydrothermal reaction of CuBr2 with NA（NA=nicotinic acid） or INA （INA =isonicotinic acid） resulted in the syntheses of two compounds [CuBr（NA）] （6） and [CuBr（INA）]∞（7） containing staircase chain. Among them the third-order non-linear optical properties of 2, 5, 6 and 7 were investigated and all exhibit the reverse saturable absorption （α2〉0） and self-defocusing performance （n2〈0）.
A new 2D (two-dimensional) coordination polymer, [Fe(μ4-bta)o.5(phen)(OH)]n (1), has been hydrothermally synthesized with FeCl3 6H2, Na4bta (h4bta = 1,2,4,5-benzentetracarboxylic acid), 1,10-phen (1,10-phenanthroline) and H2O as raw materials. The crystals of the compound belong to monoclinic P21/n space group, a = 1.0129(2) nm, b = 0.9265(2) nm, c = 1.5696(3) nm, β=91.37(3)°V=1.4721(5) nm3,Z=3, final R1=0.0292, wR 2=0.0798 for 2572 [/>2σ(/)] observed reflections. The result of structure determination shows that in the compound each bta ligand is connected with four Fe3, forming a new μ4-coordination mode. Four deprotonated carboxylic groups of bta link to Fe3 ions alternatively through monodentate and bidentate coordination fashion, constructing 2D layer network. The measurement of variable temperature magnetic susceptibility indicates that there exist antiferromagnetic interactions between Fe3 ions in the compound. The TGA spectrum displays relatively fine thermal stability of the compound. In addition, IR and UV-Vis spectra of compound 1 have also been measured.
XU Jiqing, CHU Deqing, YU Jiehui, WANG Tiegang & TANG AoqingCollege of Chemistry and State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023, China
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）.
