Synthesis, Structure And Properties Of New Inorganic-organic Hybrid Complexes Constructed From Flexible Organic Carboxylate Ligands

The aim of this thesis is the synthesis of new inorganic - organic hybrid complexes on the basis of flexible aliphatic acid, malic acid, 1, 1' - biphenyl - 2, 2' - dicarboxylate acid ligand and transitional metal ions, main metal ions, rare earth metal ions. With self assemble theory, we synthesized 29 new inorganic - organic hybrid complexes with one - dimensional, two - dimensional and three - dimensional structures. At the same time, we discussed the reaction regulation of this kind of complexes. We characterized the above complexes with elemental analysis, IR, TG and single crystal X - ray diffractions. The thermal stabilities, magnetic properties and fluorescent activities of these compounds had been studied.1. Based on flexible aliphatic acid ligands, nitrogen containing ligands and transition metal ions, we synthesized 12 inorganic - organic hybrid complexes under hydrothermal condition. In these complexes, there are two three - dimensional inorganic - organic hybrid complexes, five two - dimensional inorganic - organic hybrid complexes and five one -dimensional inorganic - organic hybrid complexes. We discussed the effects of different flexible aliphatic acid ligands on the dimensions of final products.Complexes 1 - 7 are synthesized from transitional metal ions, flexible aliphatic acid ligands and chelating nitrogen - containing ligands. Among these complexes, 1 and 2 are two - dimensional, 3 and 4 are one - dimensional, 5 is two - dimensional, and complex 6 and 7 are one - dimensional. Compared with the structures of this seven complexes, we can see, with the change of the flexible aliphatic acid ligands, the dimension of final structures are also changed.Complex 8 is one - dimensional structure. During the synthesis of this complex, we got complex 9; complex 9 is a three - dimensional pillar - layer structure. In this complex, there exist a two - dimensional Mn - O layer, which is supported by succinate acid ligand and form a three - dimensional structure. Complex 10 and 11 are iso - structure; they are both two -dimension. If we use adiphatic acid ligand replace glutarate acid ligand, we can synthesize a three - dimensional two - fold interpenetration complex 12.2. Under hydrothermal conditions, we use 1, 1' - biphenyl - 2, 2' - dicarboxylate acid, metal ions and synthesize eight inorganic - organic hybrid complexes. Furthermore, we studied the physical properties of the eight complexes.Complex 13 -17 are synthesized from different metal ions and dpa ligands. Complex 13 is a one - dimensional chain - like complex. There exists a Pb₆O₁₈ cluster in this complex, to our knowledge; the Pb₆O₁₈ cluster has never been synthesized. Complex 14 exhibits a two -dimensional structure. There exists Ag-Ag weak interaction in this complex, to our knowledge, this is the first two - dimensional complex constructed from metal ions and dpa ligands. Complex 15 is also a one - dimensional complex constructed from bi - nuclear Zn cluster. Complex 16 and 17 are iso - structure, they are all two - dimensional supramolecular network constructed from one - dimensional chains.If we introduce the second nitrogen ligand in the system, we got new complexes 18 - 20. Complex 18 is a discrete complex, which is extended to three - dimensional supramolecular network. Complex 19 exhibits a two - dimensional covalent network. Complex 20 is a three -dimensional covalent network constructed meso - helical chains.3. Based on malic acid, nitrogen containing ligands and transitional metal ions, we synthesized six new inorganic - organic hybrid complexes under hydrothermal conditions.Complex 21 is a two - dimensional layer structure, if we simplified this network, we can get a 4.8² topology. Complex 22 is also a two - dimensional layer structure. During the synthesis process, the malic acid lost hydroxyl group and form fumarate acid ligand and we synthesized complex 23. Complex 23 is a three - dimensional two - fold interpenetration network. Complex 24 - 26 are all one - dimensional chain - like structures. During the synthesis of these three complexes, the malic acid lost hydroxyl group and form fumarate acid.4. Finally, we synthesized three new inorganic - organic hybrid complexes with high nuclearity.There exist one C04 cluster in complex 27; this is a three - dimensional structure. If we simplify this complex, we can get a CaF₂ topology network. In the CaF₂ network, the Co₄ cluster act as an 8 - connected knot and 1, 2, 4 - BTC ligand act as a four - connected knot. In complex 28, there exist two kind of building unit, One is Cu(â… )₄Br₄, the other is Cu(â…¡)₃, to our knowledge, inorganic - organic hybrid complex constructed from Cu(â… )₄Br₄ and mixed Cu is seldom been synthesized. In complex 29, there exist a Cu(â… )₆Cl₆ building unit, the Cu(â… )_gCl₆ building unit connected with two Cu(â…¡)Cl(1, 10' - phen) units and extended to form a one -dimensional tap - like structure. The coordination polymers constructed from Cu(â… )₆Cl₆ and Cu(â…¡) unit is never been found. Complex 29 is the first example.