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.
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.
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.
