Four novel Cu(Ⅰ) complexes,[Cu(o-PYO)(PPh3)2]BF4(1),[Cu(o-PYO)(DPEphos)]BF4(2),[Cu2 (o-PYO)(PPh3)3(CH3CN)](BF4)2(3) and [Cu2(o-PYO)(DPEphos)2 ](BF4)2(4) (o-PYO=2,5bis(pyridyl)-1,3,4-oxadiazole,PPh 3=triphenylphosphine,DPEphos=bis(2-(diphenylphosphanyl)phenyl)ether),have been synthesized and characterized by 1 H NMR,elemental analysis and single-crystal X-ray diffraction.The central cuprous ions in all complexes are surrounded by N and P atoms to form a distorted tetrahedral geometry,although one of the cuprous ions in complex 3 is coordinated by a PPh3 and an acetonitrile molecule due to the steric hindrance and weak coordination ability from monodentate PPh3 ligand.The UV-vis absorption spectra in CH2Cl2 show the characteristic metal-to-ligand charge transfer (MLCT) absorption bands in the region of 360-480nm.Four Cu(I) complexes exhibit yellow to orange-red phosphorescence with the emission maximum at 572,577,562 and 597nm,respectively in the solid state.
The title compound,[Cu4I4(C4H8N4)4],has been synthesized and characterized by single-crystal X-ray diffraction analysis.It crystallizes in monoclinic,space group Pbca,with a=18.1851(10),b=9.3697(5),c=19.8034(10),V=3374.3(3)3,C16H32Cu4I4N16,Mr=1210.34,Z=4,Dc=2.383 g/cm3,μ=6.183 mm-1,F(000)=2272,S=1.032,the final R=0.0309 and wR=0.1180 for 3854 observer reflections(I>2σ(I)).The structure of the title compound consists of tetranuclear copper cluster units bridged by the halogen atoms with the 3,5-dimethyl-4-aminotriazole ligands coordinated to the metal ions through the triazole nitrogen atoms.The luminescent property of 1 was also studied.
Two new polyoxomolybdate compounds,namely CuII2(HL)3]2[Mo8O26]·(H2O)4(1) and [NiII(HL)3]2(Mo8O26)·(H2O)3(2)(HL = 3-(2-pyridyl)pyrazole),were designed and synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that compound 1 consists of one β-Mo8O264-cluster and a Cu2 dimer which is built from two Cu(II) ions linked by three 3-(2-pyridyl)pyrazole ligands.Compound 2 is generated by two kinds of polyoxomolybdate clusters of α-[Mo8O26]4-and β-[Mo8O26]4-.In complexes 1 and 2,the multi-dimensional frameworks are con-structed with the help of hydrogen-bonding links between the terminaloxygen atoms of [Mo8O26]4-,water molecules,and 3-(2-pyridyl)pyrazole ligands.Crystal data of 1:C24H25Cu2Mo4N9O15,Mr = 1190.37,monoclinic,space group P21/c,a = 10.850(2),b = 18.510(4),c = 17.230(3) ,β = 100.57(3)°,V = 3401.6(12) 3,Z = 4,Dc = 2.324 g/cm3,F(000) = 2312,μ = 2.742 mm-1,R = 0.0302 and wR = 0.0775(Ⅰ > 2σ(Ⅰ));Crystal data for 2:C48H48Mo8N18Ni2O29,Mr = 2225.98,monoclinic,space group P21/n,a = 20.799(2),b = 14.7970(13),c = 23.141(2) ,β = 91.6180(10)°,V = 7119.0(11) 3,Z = 4,Dc = 2.077 g/cm3,F(000) = 4344,μ = 1.968 mm-1,R = 0.0309 and wR = 0.0696(Ⅰ> 2σ(Ⅰ)).
A novel compound, {[Y(HPIDC)(OX)1/2(H2O)]·2H2O}n (1, H3PIDC = 2-(pyridin-4- yl)-1H-imidazole-4,5-dicarboxylic acid, H2OX = oxalic acid), has been synthesized under hydrothermal conditions and characterized by thermal analysis (TGA), powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction. Complex 1 crystallizes in monoclinic space group P21/c with a = 8.342(8), b = 14.61(1), c = 11.487(1), β = 90.78(9)°, V = 1400.4(2)3, Z = 4, C11H11N3O9Y, Mr = 418.14, Dc = 1.983 g/cm3, F(000) = 836, Rint = 0.0509, T = 293(2) K, μ = 4.240 mm-1, the final R = 0.0477 and wR = 0.1125 for 2770 observed reflections with I > 2σ(I). Compound 1 exhibits a 3D framework and generates the 1D open channels filled with free water molecules. The structure of 1 can be rationalized as a diamondoid network when the atom yttrium is regarded as a 4-connected node linking four surrounding yttrium atoms. The luminescent property of compound 1 is also investigated.
A new wave-like infinite chain coordination polymer [Cu3(CN)3(PPh3)4]n(1,PPh3=triphenylphosphine) has been synthesized by solution reaction and characterized by X-ray single-crystal structure diffraction analysis.The complex crystallizes in space group P1 with a=13.343(6),b=13.429(7),c=20.694(10),α=103.163(4),β=96.704(5),γ=101.981(6)o,V=3479(3)3,Z=2,C75H60Cu3N3P4,Mr=1317.76,Dc=1.258 g/cm3,F(000)=1356,μ=1.043 mm-1,the final R=0.0680 and wR=0.1305 for 9232 observed reflections with I>2σ(I).The infinite chain is linked by C-H…π H bonding interactions to form a 2-D supramolecular network.Luminescent study reveals that the complex has green-light emission.
