Syntheses And Properties Of Complexes Constructed By Multiple-P-Containing Ligands

Multiple-P-containing ligands possess good coordination capability, versatile coordinated modes and provide several donor atoms and flexible molecular deformation. The resulting complexes can be widely applicated in medicine, catalysis and optical materials. Therefore, designing multiple-P-containing ligands with different sizes and contrasting with metal salts could not noly enrich their structural chemistry, but also exploit self-assemble rules in complexes and explore novel functional compounds. In this thesis, we selected a flexible tetra-phosphine ligandN,N,N',N'-tetra(diphenylphosphanylmethyl)ethylene diamine (dppeda),and quasi-rigid tetraphosphine ligand N,N,N',N'-tetra(diphenylphosphanylmethyl)-p-phenylene diamine(dpppda) to react with CuI; and synthesized an heterobidentate P-containing ligand N-diphenylphosphanylmethyl-4-aminopyridine (dppmapy) to react with AgX (X = CN, dca, SCN, Cl, Br, I) and silver oxy-salts. We got twelve 1D, 2D coordination polymers and binuclear complexes. Their photoluminescent properties were also investigated. The contents of this thesis are described as follows:1) The syntheses of structures, and applications of four organic phosphines ligands and P,N-containing ligands were reviewed.2) The reactions of dppeda and dpppda with CuI afforded two 1D coordination polymers, {[Cu2I2(dppeda)]·(CH3CN)2}n (1) and {[Cu4I4(dpppda)]·CH3CN}n (2). In compound 1, [Cu2I2] cores and dppeda alternatively constructed to form 1D chain extending along b axis. The ligands dppeda showed end-to-end coordination mode. While in compound 2, stair-like [Cu4I4] cores and dpppda alternatively constructed to form 1D chain extending along a axis. The ligands dpppda exhibited side-by-side coordination mode.3) We synthesized a novel P,N ligand N-diphenylphosphanylmethyl- 4-aminopyridine (dppmapy). The ligand reacted with AgX (X = CN, dca, SCN, Cl, Br, I) to form five coordination polymers and one binuclear compound. Compound 3 is a 1D spiral chain. Compound 4 and 5 are 1D double chain which constructed by 16-membered rings (4) and 20-membered rings (5). Compound 6 is a 1D double helical chain containing 20-membered rings (6). Compound 7 possesses a 2D (4,4) network extending along bc plane consisting of 36-membered metallomacrocycles. Compound 8 is a binuclear compound. In compound 3-7, dppmapy works as bridge ligand. While in compound 8, dppmapy is only monodentate ligand. The photoluminescent spectra of 3-8 show that as the decrease of electron-withdrawing ability of anions, the emission maxima is gradually red-shifted.4) The reactions of dppmapy with CH3COOAg, AgNO3 and AgClO4 produced one 1D coordination polymer {[Ag2(μ-CH3COO)2(dppmapy)2]·2MeOH}n (9), one 2D supramolecule {[Ag4(NO3)2(dppmapy)4](NO3)2·MeOH} (10) and one binuclear complex [Ag2(dppmapy)2](ClO4)2 (11). In compound 11, each Ag adopted unsaturated linear coordinated mode. Therefore it is used as a precursor to react with appropriate AgCl and produced a 2D (6,3) network coordination polymer {[Ag6Cl4(dppmapy)6](ClO4)2·2MeOH·CH2Cl2}n (12). Besides of this, the [Ag2(dppmapy)2]2+ ring is oridinary in compounds 9-12, which is likely a potential precursor for further assembly.