Study On Design,Synthesis And Structures Of Complexes Constructed From Two Novel Pyridylamino Ligand

In recent years, the most important subjects of intensive current research in coordination chemistry, supramolecular chemistry, biochemistry, crystal engineering and material chemistry have been focused on the rational design, syntheses, crystal structures and properties of functional supramolecular compounds, especially the coordination polymers. The reason is not only in their fascinating structural diversity, but also in their potential applications in the fields of optical, electronic, magnetic, catalytic, molecular recognition, absorbent, ion exchange, gas storage and biology activity. Lately, it is demonstrated that considerate selectively controlling inorganic building units and creating strategies of assembly are the key in constructing target polymers and is one of the most challenging issue facing scientists either. In this research, two novel pyridylamino ligands and ten new complexes have been prepared by several kinds of methods, for instance, conventional solution, diffusing methods and hydrothermal reaction methods, also their crystal structures and properties were determined . In this paper, the main results are as follows:First, the pyridylamino ligand 2,4-di(2-aminopyridine)-6-methylpyrimidine (dapmp)(l) and its three complexes: [Cu(dapmp)Cl2](2), [Cu(dapmp)(CH3COO)2] ·H2O(3) and [Cd(dapmp)(BDC)]n(4) have been prepared and characterized by X-ray single crystal diffraction analysis, elemental analysis, IR spectra, UV-Visible spectroscopy, fluorescence and thermal analyses.The results show that dapmp and its complexes 2-4, exhibits all-anti conformation and different second ligand results in different supramolecular structures. The adjacent dimeric units dapmp(1) are interlaced and are connected by two hydrogen bonds(N-H…N), forming a 1-D supramolecular compound along c axis. In complex 2, when chloric anion is used as second ligand, the symmertric dimers are connected to be a 1-D supramolecular chain along the c axis via two self-complementary donor/accepter groups Cl…H-N bridges. As acetic anion to be the second ligand, complex 3 exhibits a 3D supramolecular network with chanels. However, Complex 4is constructed into 1D chain along the b axis by self-assembly of benzene-1,4-dicarboxy late, and each pairs of 1D chains recognize each other througharomatic π -π stacking interactions and hydrogen bonds (N-H…O) to generatedouble-chain and 2D supramolecular network with channels.Secondly, a pyridylamino ligand 2,6-(N, N'-di(4-pyridyl)amino)pyridine (tpda) (5) and its five complexes: Cu2(tpda)2(CH3-CH=CH-COO)4·H2O(6), {[Cu(tpda) (CH3COO)2]·HCCl3}n(7),{[Cu(tpda)(CH3COO)2]·CH3CN}n(8),{[Cu(tpda)(CH3COO) 2]·0.25CH2Cl2}n(9), {[Zn(tpda)Cl2]·H2O}n(10) have been prepared and characterized by X-ray single crystal diffraction analysis, elemental analysis, IR spectra, UV-Visible spectroscopy, fluorescence, magnetic investigation and thermal analyses.It is demonstrated that the second ligands and metals play important roles in various coordination polymers structures. Ligand tpda(5) is constructed into a 3D supramolecular network by hydrogen bonds. As crotonic anion is the second ligand, complex 6 connected by two bridging ligands tpda and yielded a dinuclear macrocycle, which consists of 28 atoms. When using the acetic anion as the second ligand, a series of ID polymer [Cu(tpda)(CH3COO)2] generate 3D supramolecular networks with open channels by self-assembly. After adsorbing small organic molecules CHCl3, CH3CN and CH2CI2, three complexes: {[Cu(tpda)(CH3COO)2]·CHCl3}n(7)){[Cu(tpda)(CH3COO)2]·CH3CN}n(8) and{[Cu(tpda)(CH3COO)2]·0.25CH2Cl2}n(9) are produced respectively and the guest molecular have effect on the coordination polymers structures correspondingly. When CHCl3 and CH2Cl2 act as guest, [Cu(tpda)(CH3COO)2] exhibits as a 1D helical chain with double-direction bridged by ligand 5. However, when the CH3CN serves as guest, [Cu(tpda)(CH3COO)2] gives a 1D Zigzag chain. This kind of polymers may be the third adsorptive materials in future. Complex {[Zn(tpda)Cl2]#H2O}n(10) construct a 1D neutral S-chain along the b axis by self-assembly with ligands 5, and each pair of 1D chain recognize each other through aromatic π-π stacking interactions (face to face 3.82(1)A) generating a double-chain and 2D supramolecular network with channels.The temperature-dependent magnetic susceptibility of 6 indicates that there exists weak ferromagnetic interaction between copper atoms in the dinuclear units, while which of 7 indicates that weak antiferromagnetic interaction between copper atoms in the dinuclear units.Thirdly, complex Ni(mal)(dpa)2]·((CH3CH2)2O)0.5(11) is a mononuclear complex and the copper atoms have distorted octahedral environment. Each monocuclear molecules are constructed with the neighbor ones through double-hydrogen bonds resulting in a linear supramolecular. Complex[Fe2(phen)4(μ-OH)Cl2]·(H2O)4·(CH3OH)2(12) is a ferric dinuclear compound, which is bridged by μ-OH as well as lattices H2O and CH3OH showing 1D chain via hydrogen bonds.