Silver(I) Complexes With A P-N Hybrid Ligand And Oxyanions: Synthesis, Structures, Photocatalysis And Photocurrent Responses

Ag(I) atom has been a focus in coordination chemistry for its rich coordination modes. The reactions of silver oxysalts with different ligands give rise to amounts of silver-oxo clusters which have promising applications in biomedicines, organic optical materials and photocatalysis. In this thesis, a P-N hybrid ligand N,N-bis(diphenylphosphanylmethyl)-3-aminoprydine(3-bdppmapy) was designed and selected to react with silver oxysalts. Seven new silver-oxo cluters were separated and structurally determined. 3-bdppmapy, 6, 7 were selected and their catalytic activities toward the photodegradation of organic pollutants in aqueous solutions were investigated. The main contents of this thesis are described as follows:(1) A minireview has been made on silver-oxo clusters and their applications in photocatalysis.(2) Evaporation, diffusion and solvothermal reactions of silver oxysalts with 3-bdppampy gave rise to seven silver-oxo clusters, {[Ag4(μ-η,η-NO3)2(μ-η,η2-NO3)2](3-bdppmapy)2}n(1), {[Ag4(μ-η,η2-NO3)4](3-bdppmapy)2}n(2), {[Ag2(μ-η2-OAc)(μ-η,η2-OAc)]2(3-bdppmapy)2}n(3), [Ag2(Bz)(μ-η,η2-Bz)(H2O)]2(3-bdppmapy)2(4), {[Ag4(μ-η2-Bz)2(μ-η,η2-Bz)2](3-bdppmapy)2}n(5), {Ag(Sal)(3-bdppmapy)}n(6) and {[Ag4(Sal)2(μ-η,η2-Sal)2](3-bdppmapy)2}n(7), respectively. 1–7 were characterized by elemental analyses, IR, powder X-ray diffraction, 1H NMR, 31 P NMR, thermal-gravity analyses, and single crystal X-ray diffraction analysis. Compound 1, 5, 6, 7 have 1D chain structure, 2 and 3 presents a 2D planar structure while 4 has a tetranucler structure. 6 is connected by AgSal molecules and single 3-bdppmapy bridges while the others are composed of silver-oxo clusters and 3-bdppmapy bridges. 1, 5, 7 are contructed by [Ag4(Ox)4](Ox = Oxysalt anion) clusters and 3-bdppmapy bridges. 2 and 3 contain the [Ag4(NO3)4] or [Ag2(OAc)2] cluster and 3-bdppmapy bridges. 4 is formed by two [Ag2(Bz)2(H2O)] clusters and the double 3-bdppmapy bridge.(3) The photodegradation of rhodamine B(RhB) as well as tetracycline and ceftriaxone sodium under UV light were investigated by using 3-bdppmapy, 6, and 7 as catalysts. The catalytic photodegradation reactions exhibited the zero-order kinetics character and indicated the increasing efficiency toward photodegradation. The mechanism of the photodegradation reactions were supposed to be the ·OH radical mediated route. The catalysts were stable during the catalysis. Photocurrents and Density function theory(DFT) calculations of their HOMO-LUMO gaps were carried out to study the impact factors of their catalysis.