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 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 ℃.
Temperature dependent assembly of two novel Cd coordination polymers with the phen and H2MIP ligands （phen = 1,10-phenanthrolion and H2MIP = 5-methyl-isophthalic acid）, formulated as Cd2（MIP）2（phen）2 （1） and Cd3（MIP）3（H2MIP）（phen）2 （2）. They have been structurally characterized by single-crystal X-ray diffraction, elemental analysis, FT-IR spectra and TGA. 1 crystallizes in the monoclinic space group P2/n, while 2 crystallizes in the triclinic space group P1. 1 shows a 2D （two-dimensional） plane and 2 shows a 1D （one-dimensional） chain. In addition, their solid-state luminescent properties have also been investigated.
Two homochiral enantiomorphic 3D coordination polymers： （D-HAPA）2[Cd2Cs（D- HAPA）（m-BDC）4]＇（EtOH） （1D） and （L-HAPA）2[Cd2Cs（L-HAPA）（m-BDC）a]＇（EtOH） （1L） （APA = 2-amino-l-propanol, m-H2BDC = 1,3-benzenedicarboxylate）, have been assembled solvothermally respectively with the induction of enantiomorphic organic small molecules （D,L-APA）. 1L and 1I） crystallize in chiral space group P21 with Flack parameters of-0.012（13） and -0.07（3）, respectively, and have been characterized by satisfactory elemental analysis, FT-IR spectra, CD-spectra and single-crystal X-ray diffraction. They both exhibit sqp topological net, purple fluorescence and SHG activity.
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%.
Presented here is the solvothermal preparation of two luminescent coordination polymers （L-CPs） based on the same mixed ligands, namely [Cd2（1,4-NDC）2（dppe）] （1） and [Mn3（OH）2（1,4-NDC）2（dppe）（H2O）] （2） （1,4-NDCH2 = 1,4-naphthalene dicarboxylic acid, dppe---- 1,3-di（4-pyridyl）propane）. Both the title compounds feature a neutral three-dimensional （3D） network. Photoluminescence （PL） studies indicated that the compound 1 based on d10 Cd2＋ exhibited dual emissions with tunable intensities that could result in direct white-light emission based on the in- traligand charge transfer （LLCT）; while the compound 2 showed a single band of yellow emission based on the charge transfer between the ligands and the metal ion （LMCT）, due to the partially filled d-orbital of Mn2＋ ion. The temperature-dependent powder X-ray diffraction patterns （PXRD） and PL spectra were further measured to identify their thermal stabilities. This work may provide a certain guiding significance for exploiting L-CPs based on different metal ions.
