| Coordination Polymers are constructed from the metal ions or clusters asthe nodes and the ligands as the liners. As a unique class of novel functionalmaterials, they not only exhibit numerous fascinating structures, but also havepotential applications in gas storage, adsorption and separation, catalysis,luminescent, magnetic and so on. Second building unit (SBU) is one way ofconstructing this kind of coordination polymers. Remarkable progress has beenmade in design and synthesis the ligands which have fixed geometry, while theresearch on exploring the inorganic SBUs is less. Our group used5,5'-(1,2-ethynediyl)bis(1,3-benzenedicarboxylic acid)(H4EBDC) and its elongated5,5'-(buta-diyne-1,4-diyl) diisophthalic acid (H4BDDC) as the ligands, bychanging the ratio of the reactants, the polarity of the solvent, the temperatureand the organic bases, successful synthesized twenty eight new compoundsunder solvothermal conditions. The structures and the topologies of thesecompounds have been discussed, together with their corresponding properties,such as gas storage, luminescent and magnetic. The research presented hereinfocuses primarily on the following aspects:1. Five indium based compounds with different topologies have beensolvothermal synthesized by employing H4EBDC as organic ligands.Compounds1-2are both constructed by the tetrahedral inorganic SBU [In(RCO2)4] and four connected rectangular organic ligand. However, theypresent different topologies, compound1has4-connected pts topology, whilecompound2is exhibiting new topology. From a topology analysis, compound1has two independent nodes, and the vertex symbols are4.4.8(2).8(2).8(8).8(8)and4.4.8(7).8(7).8(7).8(7), while compound2is more complex and containsfour independent vertices with corresponding vertex symbols of4.4.8(2).8(2).8(8).8(8),4.6(2).6(2).8(8).8(2).8(2),4.4.6.8(7).6.8(7),4.6(2).6.8(7).6.8(7). Secondly, we have constructed six-connected [In3O(CO2)6]SBUs, assembled with the organic ligand H4EBDC to build different compounds.compound3has soc topology, the inorganic SBU can be rationalized as a6-connected trigonal prismatic building unit and can be regarded as a octahedron,the4-connected node is represented by the organic ligand, H4EBDC, which isrationalized as rectangular-planar node, accordingly, the assembly of such4-and6-connected nodes results in the formation of an edge-transitive3-periodicnetwork with soc topology. It is worth to mention that there are two differentinorganic SBU in compound4:[In(RCO2)4] and [In3O(RCO2)6] SBUs, these twodifferent inorganic SBUs connected through the ligand H4EBDC to buildcompound4with new topology, compound5also exhibits a new structure, andit is constructed from the [In3O(RCO2)6] SBUs and the organic ligand H4EBDC.As the compounds3-4have high thermal stability and large pores, weinvestigated their adsorption properties.2. Fourteen novel lanthanide coordination polymers of varying dimensionality and topologies have been prepared and characterized under solvothermalconditions, Nb2(EBDC)(NO3)(DMF)2(6), Eu2(EBDC)(NO3)(DMF)2(7),Tb2(EBDC)(NO3)(DMF)2(8), Er2(EBDC)(NO3)(DMF)2(9),Yb2(EBDC)(NO3)(DMF)2(10), Yb(EBDC)(G)(11), Er2(EBDC)(NO3)(DMF)2(12), Yb2(EBDC)(NO3)(DMF)2(13) and Tb2(EBDC)(DMF)2(G)(14),Yb2(EBDC)(DMF)2(G)(15), Eu(HEBDC)(DMA)(H2O)2(16),Tb(HEBDC)(DMA)(H2O)2(17), Eu(H2EBDC)(DMF)2(H2O)(G)(18), andTb(H2EBDC)(DMF)2(H2O)(G)(19). The series of Ln-MOFs are with pts(compounds6-10), nbo (compound11), lvt (compounds12-13), and kgd(compounds16-17) topologies, respectively. In the compounds with pts, nbo andlvt topologies, the dinuclear Ln-ions formed four square connected nodes,interestingly, the organic ligand H4EBDC in the compounds with pts topologychanged into a tetrahedral four connected node, the side phenyl rings bearingtwo carboxylate groups in H4EBDC twist around the middle ethynyl to form atetrahedron. The compounds with kgd topology were constructed from6-connected inorganic SBUs and3-connected organic ligand. Besides thementioned above, we also synthesized a dinuclear Ln-ions which can besimplified into8-connected node, the nodes connected with the four connectedligand and finally formed new topology compounds (compounds14-15).Compounds18-19are constructed from the single Ln ions and the twoconnected ligand, and finally formed the compounds with3D supermolecularnetworks. Considering the unique physical and chemical properties of the Ln ions, we also investigated the luminescence of the compounds.3. Nine novel coordination polymers based on multifunctional ligands5,5'-(1,2-ethynyl)bis-1,3-benzenedicarboxylic (H4EBDC) and5,5'-(buta-diyne-1,4-diyl) diisophthalic acid (H4BDDC), namely:Zn2(EBDC)(bipy)2(G)(20), Zn6(EBDC)3((C6H12N2O2)2(G),(21) Cd3(EBDC)2(G)(22), Mn(EBDC)(DMF)2(G)(23), Mn6(EBDC)4(G)(24), Mn2(EBDC)(DMF)2(25), Mn4(EBDC)2(G)(26), Co2(EBDC)(H2O)2(G)(27), andCu2(BDDC)(H2O)2(G)(28) have been constructed under solvothermalconditions and structurally characterized by single-crystal X-ray diffraction. Inthese compounds, the ligand H4EBDC exhibits different coordination modes andconformations, constructing various architectures by bridging a variety of metalions or polynuclear clusters. Compound20forms a3D fsc network constructedfrom2D layer motifs joined by EBDC4-and4,4'-bipy bridges, compound21possesses a nbo topology by linking Zn2(CO2)4units with the ligand,coordinated amine molecules fill in the pores, while compound22exhibits a3Dflu network with Cd2+as the cation features infinite framework built fromtricadmium cluster. Compound23is based on pts net, constructed of4-connected rectangular H4EBDC unit with tetrahedral monometallic Mn(CO2)4SBUs, compound24shows a2D layer with (3,6)-connected kgd topology, andcompound25presents a3D pts-x network, built by bridging a metal chain withthe ligand. Compound26also exhibits pts topology, however, the inorganicSBU is constructed by four crystal independent Mn ions, and the finally structure of compound26is different from the compound23. Compound27alsoexhibits nbo topology, which is constructed by the nitrate cobalt and H4EBDCligand. Compound28has been synthesized by employing H4BDDC as organicligand, and the topology is nbo network. The structures of these compoundshave been discussed, as well as their corresponding properties: gas storage,separation, and magnetic properties.
|
PDF Full Text Request