Synthesis, Crystal Structure And Properties Of Several Carboxylate Coordination Polymers And Drug Chiniofon Complex

In recent years, much attention has been paid to the designs, syntheses, crystal structures and properties of the carboxylic acid coordination polymer, due to the extensive application of the carboxylic acid coordination polymer, such as non-linear optical materials, magnetic materials and coating materials. The methods usually used are conventional solution and hydro(solvo)thermal reaction methods. In this research, eight new coordination compounds have been designed and synthesized, with all of them studied systematically by Elemental Analysis, IR and single crystal X-ray diffraction. The results show that the synthesized complexes can be divided into three types, that is one-dimensional (1-D), two-dimensional (2-D) and three-dimensional (3-D) systems. Their crystal structures and spectral properties were characterized. Chapter one: Compound C17H17.50N2O5Zn(1) belongs to monoclinic crystal system, space group C2/m, with the parameters: a=9.7462(17)a, b=19.627(3)a, c=10.3287(18)A, V=1943.5(6)A³, Z=4, Dc=1.351Mg m^-3. In 1, the center metal Zn(â…¡) adopts distorted octahedral geometry. The Zn (â…¡) is six-coordinated and surrounded by five oxygens, four from carboxylate of 3,3'-ABD and one from the ethanol molecule. At the same time, the center Zn (â…¡) coordinates with the other Zn (â…¡). In the unit, there is weak metal-metal bond. The compound is a two-dimension net complex of infinite length connecting with bridging oxygen from carboxylic acid. Co3(CH3CO2)2[(3,3'-ADB)2](C12H8N2) (2) belongs to triclinic crystal system, space group P-1, with the parameters: a=10.3958(13)?, b=11.3170(15)?, c= 11.5539(15)?, V=1244.4(3)?3,Z=1, Dc=1.590 Mg m-3. In this complex, trinuclear unit link by the carboxylate group and exihibit ground different coordination mode. Sharing corners of the trinuclear units forms an infinite 2D-network with pores of 17.023×15.998 ?2. In complex 1 and 2, there exist nano-size pores, which can possibly absorb some small molecules such as water, benzene and offer them potential applications in microporous material. Chapter two: Pb(C14H8N2O4)(phen)(3) belongs to triclinic crystal system, space group P-1,with the parameters: a=9.8207(13)?, b=11.2083(10) ?, c=11.8496(11)?, V=1093.9(2)?3, Z=2, Dc=1.991 Mg m-3. The Pb(??) adopts distorted octahedral geometry with six coordination numbers. The Pb(??) center is surrounded by four O atoms from carboxylate group and two N atoms from phen. The adjacent lead(??) atoms are linked by two carboxylate group through didentating mode, simultaneously chelates two N atom of the phen to form a stable five-numbered ring. Through the bridging 3,3'-ADB ligand, the builing blocks further constructed one-dimensional coordination polymer. In the same reaction condition, we synthesis a novel coordination complex of Mn2(C14H8N2O4)(CH3COO)2(phen)4 (4) belongs to triclinic crystal system, space group P-1,with the parameters: a=10.8897(8) ?, b=11.0811(3) ?, c=14.3303(14)?, V=1445.29(18)?3, Z=1, Dc=1.440 Mg m-3. In the complex 4, the Mn (??) ion adopts octahedral geometry with six coordination numbers. The Mn (??) center surrounded by four N atoms from phen and two O atoms, one O atom from carboxylate group and the other O atom from acetic group. The four N come from two phen. The center Mn (??) chelates four N from two phen to form two stable five-number rings. Variabletemperature magnetic susceptibility measurements reveal that the presence of an antiferromagnetic interaction between the Mn(??) centers in complex 4. Chapter three: [Ni2(HCOO)6]·(CH3CH2OH)2 (5) belongs to trigonal crystal system, space groupR-3,with the parameters: a=8.1150(8)?, b=8.1150(8)?, c=21.939(3)?, V=1251.2(2)?3, Z=2, Dc=1.910 Mg m-3. Compound 5 was prepared by the hydrothermal treadment of Ni(ClO4)2 with 3,3'-Azodibenzoic acid in the presence of DMF, H2O, EtOH and NaOH. The Ni (??) adopts six-coordinated distorted octahedral geometry and surrounds by six oxygen atoms from formyl carboxylate group. Through the bridging carboxylate group, compound 5 forms 3D network. Chapter four: [Ni(C9H4INO4S)2(H2O)3]2?H2O(6) belongs to triclinic crystal system, space group P-1, with the parameters: a=10.9187(4)?, b=11.32290(10)?, c=13.6994(6)?, V=1392.50(8)?3, Z=2, Dc=2.246Mg m-3. The Ni (??) adopts six-coordinated distorted octahedral geometry. Two inversion-related ligands and two Ni (??) atoms form a cage-like dimmer. Two inversion-related Ni-O (sulfonate) bonds form a dimmer. The octahedral coordination geometry of nickel (??) is made up of the ring N atom, the deprotonated quinolinol O atom, one of the sulfonate O atoms, and three water molecules .The ligands in the dimmer are stacked over one another. X-ray crystallographic analysis indicates the compound 7 is very similar to compound 6. The zinc atoms are six-coordinated octahedral geometry. The complex 7 exhibits intense green fluorescence when it is irradiated by UV-Vis light in solid state at room temperature. C21H23I2N4O13S2Sm (8) belongs to triclinic crystal system, space group P-1, with the parameters: a=8.0211(6)?, b=10.2643(9)?, c=18.4156(19)?, V= 1477.2(2)?3, Z=2, Dc=2.266Mg m-3. In the complex 8, the Sm (???) is seven-coordinated pentagonal bipyramid geometry. The pentagonal bipyramid Sm (???) is composed of two N atoms, two O atoms both from the chiniofon, one of the sulfonate O atom and three water molecules. One-dimensional infinite-chain of complex 8 is formed through bridge chiniofon.