Synthese,Crystal Structures And Properties Of Metal-Organic Frameworks Based On(3,5-dicarboxylphenoxy)benzoic Acid Group

In this thesis,we used two different flexible carboxylate ligands,3,5-bis(3,5-dicarboxylphenxoy)benoic acid(H5L)and 3-hydroxyl-5-(3,5-dicarboxylphen xoy)benoic(H3L'),and solvothermally synthesized five metal-organic frameworks(MOFs)based on H5L and two metal-organic frameworks based on H3L' with transition metal salts Cu(?)?Zn(?)?Cd(?)and lanthanide metal salts Tb(III)?Dy(III).They are shown as follows:[Cu5L2(H2O)5]·1OH2O10ODMF(1)[Cu5L2(H2O)5]·10DMA(2)[Cd5L2(H2O)6]·4H2O·3DMF(3)[Zn5L2(H20)5]·11H2O·8DMA(4)[Zn3L(H20)3(OH)]-4H20·5DMF(5)[DyL'(H20)]3H2O·DMA(6)[TbL'(H20)]-3H20-DMA(7)The crystal structures of 1-7 were characterized by single crystal X-ray diffraction analyses,power X-ray diffraction,thermogravimetric analysis,FTIR and elemental analysis.1 and 2 are all crystallize in the tetragona1 I4/mmm space group.But 1 and 2 have different three-dimensional network structure,1 is composed of three different kinds of cage structures,and the guest-accessible void volume is 65.30%.2 is only a kind of cage structure,and the guest-accessible void volume is 63.52%.Furthermore,the gas adsorption performance of 1-2 were investigated,they featured different adsorption and separation properties for various gas of N2?C2H2?CH4?CO2.Compared to 1 and 2,1 has better adsorption performance and is more suitable for application in the C2H2/CH4 and CO2/CH4 gas separation materials.3 crystallizes in the monoclinic C21/c space group,and exhibits a(4,8)-connected 3D network with Schlafli symbol of(410·615·83)(45·6)2.4 crystallizes in the tetragonal I4/mmm space group.5 crystallizes in the orthorhombic Pmn21 space group,and exhibits a(4,4)-connected 3D network with Schlafli symbol of(66).3-5 are all 3D network structure,and the guest-accessible void volume are 14.01%?64.41%and 66.44%,respectively.Furthermore,the luminescent properties of 3-5 were investigated.In comparison with the H5L ligand,3-5 generated blue shift obviously.Based on H3L ligand,two lanthanide organic frameworks were synthesized:[LnL(H2O)]-4H2O·DMA(Ln = Dy(6),Tb(7)).X-ray single-crystal structural analyses revealed that these MOFs are isostructural except the lanthanide ions used.They crystallize in the orthorhombic crystal system,Ibca space group.They show 1D inorganic chain connected by[Ln3(COO)2]SBUs,which were paralleled to b axis with its left or right hand spiral structure.Further to form an extended 3D network linked together via L3-ligands.The different luminescent response to small molecules of 7 was studied.The results show that 7 has different luminescent response to different small molecules.