Studies On The Syntheses And Crystal Structures Of The Complexes Bridged By The Ligand Of 4, 4'-Bipyridine

4, 4' - Bipyridine is an excellent riid bridging ligand, and it is liable to have some weak intermolecular interaction such as hydrogen bonding and TI-TT stacking effect with other molecules. It is essential to study the syntheses, crystal structures of the complexes formed by the ligand of 4, 4'-bipyridine systematically, and to inquire into the factors that influence the formation and structures of the complex containing 4, 4'-bipyridine. Not only can it lead to design and synthesize all kinds of functional materials, but also it may provide some reliable theoretical foundations for the newly born supramolecular chemistry and crystal engineering.More than ten new complexes bridged by the ligand of 4, 4'-bipyridine (4, 4'-bpy) have been synthesized in different mixed solvents. Ten single crystals were obtained and eight of them were studied by x-ray diffraction. From these complex structures, the bridging function of the ligand of 4, 4'-bpy in transition metal complexes, rare earth complexes and heteronuclear complexes containing transition metal and rare earth metal simultaneously was studied systematically. At the same time, a further study about how the counter-anion of picric (pic"), which has big volume and poor coordination ability, affects the formation and structures of the complex formed mainly by metal ions and 4, 4'-bpy molecules. And our research work demonstrates that there are also other factors affect the formation and structures of the complex containing 4, 4'-bpy molecules, such as temperature and synthesis methods.The PH value of the reaction solution was strictly controlled at 5-6 in order to guarantee against the occurrence of precipitate. A novel La( III )-Cu( II) heterometallic complex [LaCu2(4, 4'-bpy)(NTA)2(H2O)3]NO3 ?5H2O(1) was synthesized by means of controlling different temperature in different step. The complex crystallizes in the triclinic space group PI with cell parameters a = 13.3710(10) A, b = 14.4530(10) A, c = 10.949(2) A, a= 71.905(7) (3 = 74.327(7) y = 64.427(9)? V = 1791.2(4) A3 and Z=2. In the title complex, La(III) ions and Cu( II ) ions are connected by the heterometallic bridging ligand of nitrilotriacetic anion(NTA3), constructing a 2-D network structure along the (110) plane. Then it is extended into an infinite 3-D network structure by the formation of homometallic bridging of Cu-4, 4'-bpy-Cu.Three complexes of the formula [Cd ( 4, 4'-bpy) 2(H2O)2]n-(pic)2ll(2), [Zn(4,4'-bpy)2(H20)2]n(pic)2n. (4,4'-bpy) (H2O)n (3) and [Zn(4,4'-bPy)2(H2O)2]n(Pic)2n.(H2O)2n (4) have been synthesized at different temperature and characterized by single crystal x-ray diffraction. Complex 2 crystallizes in the monoclinic space group C2/c with cell parameters a= 16.551(2) A, b= 16.782(2) A, c= 14.689(2) A, p=l 18.47(1) V=3587(2) A3, Z=4. Complex 3 crystallizes in the monoclinic space group Cc with cell parameters a=22.716(2) A, b= 16.191(3) A, c= 16.166(2) A, p=l31.085(7) V=4481(2) A3, Z=4. Complex 4 crystallizes in the monoclinic space group Cc with cell parameters a=14.390(2) A, b=l 1.418(1) A, c=22.908(3) A, p=95.08(l) V=3749(l) A3, Z=4. They all have infinite 2-D network structures, and the networks of complex (3) and (4) are extended into 3-D network structures by packing along the a axis through different hydrogen bondings. All of them exhibit acertain inclusion ability.The complex of the formula [Cu(4,4'-bpy)(pic)2](5) was obtained by the diffusion between two kinds of reactant solutions. It crystallizes in the triclinic space group PI with cell parameters a=6.100(2) A, b=10.!86(3) A, c=l 1.046(2) A, a =107.230(10) P =101.992(2)y =97.87(7) V=626.6(3) A Z=l,. The crystal structure comprises infinite 4,4'-bpy-bridged polymeric [Cu(4, 4'-bpy)(pic) 2] chains.A non-covalent organic molecular polymer [(phen)(phenH)(4,4'-bpyH)](pic)2 (6) was obtained by self-assembly. It crystallizes in the triclinic space group PI with cell parameters a = 7.3370(10) A, b= 10.3390(10) A, c = 15.195(2) A , a = 75.990(10)? p = 84.780(10)= 70.160( 10) V = 1051.9(2) A3, Z = 1. The intermole...