Silver-phosphine Coordination Polymers Incorporating A Wurster's Radical Cation And Their Photoelectric Properties

Free radical chemistry is closely related to reaction mechanism,material chemistry,structural chemistry and biomedicine.Most free radicals are high reactive and undergoing very short lifetime due to the unpaired electron.As one of the most stable organic free radicals,the one-electron oxidation product of p-phenylenediamine and its derivative?Wurster's radical?usually exist as free cations,which have a long history and were the earliest free radicals employed in the ESR spectroscopy studies.In this paper,we carried out the construction of coordination polymers?CPs?form silver-oxo clusters with a tetra-phosphine ligand(N,N,N',N'-tetra?diphenylphosphanylmethyl?benzene diamine?dpppda?which containing p-phenylenediamine,group.The Wurster's blue radical cation was observed due to the intramolecular charge transfer process.We also investigated their photoelectric responses.The major contents of this thesis are described as follows:1 A review on the discovery,properties and applications of Wurster's free radical cations and their derivatives was presented.2 The interdiffusion of dpppda and AgNO₃ afforded four one-dimensional CPs containing Ag₄O₄silver-oxo clusters,namely {[Ag₄?NO₃?₄?dpppda?]}_n?1,2?,{[Ag₄??₃-?³-NO₃?₄?dpppda?]}_n?3?and {[Ag₄??-?²-NO₃?₂??-?:?²-NO₃?₂?dpppda?]_n?4?,respectively.While the reactions of dpppda with AgCO₂CF₃,AgSO₃CF₃ resulted in two one-dimensional CPs containing Ag₄O₆ silver-oxo clusters {[Ag₄?CO₂CF₃?₄?dpppda?]}_n?5?,{[Ag₄?SO₃CF₃?₄?dpppda?]}_n?6?,respectively.Compounds 1-6 were characterized by EA,IR,NMR,solid-state UV-vis,Powder X-ray diffraction?PXRD?and Single-crystal X-ray diffraction?SCXRD?.The DFT theoretical calculations,XPS and ESR spectra have proved that the intramolecular ligand-to-metal charge transfer?LMCT?led to the generation of the Wurster's blue radical cations within 1-6.Under the irradiation of light??>400 nm?,the LMCT in 1-6 could be enhanced.Simultaneously,compounds 1-6 exhibited enhanced Ag????Ag?0?potentials,strong photocurrent responses and improved oxygen evolution reaction?OER?activities.