Studies On The Structure And Property Of Functional Coordination Polymers Constructed By Aryl-multicarboxylic Acid

Based on the analysis for recent progress in coordination polymers and ourgroup’s research, several aryl-multicarboxylic acid ligands were designed andsynthesized. These aryl-multicarboxylic acid ligands contain two scorpion-shapedmulti-carboxylate ligand （3,5-dimethyl phenoxyacetic acid: HDMBC and5-（carboxymethoxy） isophthalic acid: H3OABDC） and a pentaerythritol basedaryl-multi-carboxylic acid ligand （1,1,1,1-（5-hydroxy isophthalic acid-oxygenmethyl） methane: H8L）. A series of coordination compouds were synthesized by usingthese aryl-multicarboxylic acid ligands. For instanse, by using a HDMBC, a newcomplex, namely Cu （DMBC）₂（H₂O）₂（1）, were solvothermally synthesized. By usingH₃OABDC，two new coordination polymers，namely [Ni₂（OABDC）（bipy）1.5（H₂O）3]n（H₂O）3n（2） and [Ni₄（OABDC）₂（OH）₂（H₂O）₄]n（3）, were solvothermally synthesized.Three coordination polymers,[Zn₄（L）（py）6（H₂O）₂]（4）,[Co₃（L）（py）5（H₂O）₂] H₂O （5）and [Co₂（L）0.5（OH）（H₂O）]（6），was obtainted by hydrothermal reaction of metal saltand5-（carboxymethoxy）isophthalic acid synthesized by esterification, bromination,etherification, hydrolysis, etc multistep reaction of pentaerythritol. The complexescharacterized by elemental analysis and IR. The single crystal structure of thecoordination compound was determined by X-ray diffraction. Compound1is atwo-dimensional supramolecular framework and crystallizes in monoclinic P21/c spacegroup, a=15.26（2） nm, b=7.092（11） nm, c=10.942（17） nm, β=104.567（15）°，V=1146（3） nm³，Z=2，F（000）=478. In the molecular, the centric Cu（Ⅱ） ion wassituated in the center of slightly deformable quadrilateral plane element andcoordinated with two O atoms from two ligands and two water molecules. Thecompound self-assembled to2D sheet supramolecular frameworks by π-π interactionand hydrogen bonding. The quantization calculation of title complex as structure unitwere carried out at B3LYP/6-31G level with Gussian03program, and given thecharge distribution of complex molecules in the atomic. The calculation results arevery close to the measurement results. Compound2is a three-dimensional channelsframework and crystallizes in monoclinic C2/c space group, a=1.7433（5） nm,b=1.5289（5） nm, c=2.3250（7） nm, β=97.100（3）°, V=6.149（3） nm³, Z=4. Compound 3is a2-dimensional sheet framework and crystallizes in monoclinic C2/c space group,a=1.2386（18） nm, b=1.900（3） nm, c=1.369（2） nm, β=111.844（13）°, V=2.990（8）nm³, Z=4. Compound4crystallizes in the monoclinic space group of C2/c. Thepacking of the coordination polymer is complex as the remaining two arms of theerythritol assemble around the tetragonal channel in a zig-zag manner. The volume ofthe void measured from contact surfaces of the polymer with the probe radius of1.2is20.9%of the unit cell volume. About7.8%of the void is accessible to solvents.Compound5also crystallizes in the monoclinic space group of C2/c. The complexpacks with large channels of open void. About24.7%of the unit cell is vacant with8.7%of the volume accessible to solvents. Compound6crystallizes in the cubicsystem with space group Pn-3n. The complex packs with large channels of open void,about60.7%of the unit cell. Moreover, Bioassay showed that some of the compound1had high plant-growth regulatory activity. At the concentration of0.01ppm, the（compound1） exhibited stimulating activities to the root growth of rape （Brassicanapus）. The stimulating （activity） of compound1（275.2%） was higher than that ofligand. The antibacterial activity test result shows that the complex1possess stronginhibition activity to Bacillus subtilis, Proteus and Shigella. And the cyclohexene ofcatalysis and dye absorption properties of compound2were studied. Dye adsorptiontests showed that the compound2adsorption capacity for methyl orange into6.9×10-6mmol/g, the adsorption percentage is65%. Cyclohexene catalyzed tests showed thatthe compound2selective catalytic oxidation of cyclohexene was obtained as themajor product cyclohexenone, the selectivity of cyclohexenone was72.7%, and theyield could reach84.2%. And thermal properties of complex5and6were studied.Results showed that the complexes are stable before100degrees centigrade. Due totheir unique pore or a hole structure, these coordination polymers show a potentialapplication prospect in the fields of gas adsorption and ion-exchange and so on.