Atom transfer radical polymerization (ATRP) using cuprous chloride/2,2'-bipyridine (bipy) was applied to graft polymerization of styrene on the surface of silica nanoparticles to synthesize polymer-inorganic hybri...Atom transfer radical polymerization (ATRP) using cuprous chloride/2,2'-bipyridine (bipy) was applied to graft polymerization of styrene on the surface of silica nanoparticles to synthesize polymer-inorganic hybrid nanoparticles, 2-(4Chloromethylphenyl) ethyltriethoxysilane (CTES) was immobilized on the surface of silica nanoparticles through condensation reaction of the silanol groups on silica with triethoxysilane group of CTES. Then ATRP of St was initiated by this surface-modified silica nanoparticles bearing benzyl chloride groups, and formed PSt graft chains on the surface of silica nanoparticles. The thickness of the graft chains increased with reaction time. End group analysis confirmed the occurrence of ATRP. Thermal analysis indicated that thermal stabilization of these resulting hybrid nanoparticles also increases with polymerization conversion. The results above show that this 'grafting from' reaction could be used for the preparation of polymer-inorganic hybrid nanoparticles with controlled structure of the polymer's end groups.展开更多
Two novel silver（I） complexes [Ag（DPEphos）（dppe）]Cl O4（1） and [Ag（DPEphos）-（dppe）]SCN（2）（DPEphos = bis[2-（diphenylphosphino）phenyl]ether, dppe = bis（diphenylphosphino）ethane） are synthesized and ch...Two novel silver（I） complexes [Ag（DPEphos）（dppe）]Cl O4（1） and [Ag（DPEphos）-（dppe）]SCN（2）（DPEphos = bis[2-（diphenylphosphino）phenyl]ether, dppe = bis（diphenylphosphino）ethane） are synthesized and characterized by IR, 1H/31 P NMR spectroscopy and fluorescence spectra. Complex 1 crystallizes in monoclinic, space group P21/c with a = 14.8821（12）, b = 12.6620（11）, c = 36.025（3） ？, β = 112.633（2）°, V = 6265.7（9） ？3, C62H52 Cl O5P4Ag, Mr = 1144.24, Z = 4, Dc = 1.213 g/cm3, F（000） = 2352, μ = 0.510 mm-1, the final R = 0.0616 and w R = 0.1192 for 4003 observed reflections（I 〉 2σ（I））. Complex 2 crystallizes in monoclinic, space group P21/c with a = 14.9021（13）, b = 12.6100（11）, c = 35.920（3） A, β = 112.852（2）°, V = 6220.2（9） A3, C63H52NOP4 SAg, Mr = 1102.87, Z = 4, Dc = 1.178 g/cm3, F（000） = 2272, μ = 0.498 mm-1, the final R = 0.0912 and w R = 0.1706 for 3287 observed reflections（I 〉 2σ（I））. In mono-nuclear complexes 1 and 2, the Ag（I） atom is chelated by DPEphos and dppe ligand. In the 31 P NMR spectra, there are splitting signals（doublets or triplets） which can be attributed to the coupling of the 107,109Ag–31P（from DPEphos or dppe ligand）. All the emission peaks of these complexes are attributed to ligand-centered（π-π＊） transitions.展开更多
基金This project was supported by the National Natural Science Foundation of China to K.Y Qiu (Grant No. 29874002) and Outstanding Young Scientist Award to Y. Wei (Grant No. 29825504)
文摘Atom transfer radical polymerization (ATRP) using cuprous chloride/2,2'-bipyridine (bipy) was applied to graft polymerization of styrene on the surface of silica nanoparticles to synthesize polymer-inorganic hybrid nanoparticles, 2-(4Chloromethylphenyl) ethyltriethoxysilane (CTES) was immobilized on the surface of silica nanoparticles through condensation reaction of the silanol groups on silica with triethoxysilane group of CTES. Then ATRP of St was initiated by this surface-modified silica nanoparticles bearing benzyl chloride groups, and formed PSt graft chains on the surface of silica nanoparticles. The thickness of the graft chains increased with reaction time. End group analysis confirmed the occurrence of ATRP. Thermal analysis indicated that thermal stabilization of these resulting hybrid nanoparticles also increases with polymerization conversion. The results above show that this 'grafting from' reaction could be used for the preparation of polymer-inorganic hybrid nanoparticles with controlled structure of the polymer's end groups.
基金supported by the National Natural Science Foundation of China(Nos.21171119 and 81573822)the National High Technology Research and Development Program 863 of China(No.2012AA063201)+1 种基金the Technology Foundation for Selected Overseas Chinese,the Beijing Municipal Education Commission(KM201510028006)the Scientific Research Base Development Program of the Beijing Municipal Commission of Education
文摘Two novel silver（I） complexes [Ag（DPEphos）（dppe）]Cl O4（1） and [Ag（DPEphos）-（dppe）]SCN（2）（DPEphos = bis[2-（diphenylphosphino）phenyl]ether, dppe = bis（diphenylphosphino）ethane） are synthesized and characterized by IR, 1H/31 P NMR spectroscopy and fluorescence spectra. Complex 1 crystallizes in monoclinic, space group P21/c with a = 14.8821（12）, b = 12.6620（11）, c = 36.025（3） ？, β = 112.633（2）°, V = 6265.7（9） ？3, C62H52 Cl O5P4Ag, Mr = 1144.24, Z = 4, Dc = 1.213 g/cm3, F（000） = 2352, μ = 0.510 mm-1, the final R = 0.0616 and w R = 0.1192 for 4003 observed reflections（I 〉 2σ（I））. Complex 2 crystallizes in monoclinic, space group P21/c with a = 14.9021（13）, b = 12.6100（11）, c = 35.920（3） A, β = 112.852（2）°, V = 6220.2（9） A3, C63H52NOP4 SAg, Mr = 1102.87, Z = 4, Dc = 1.178 g/cm3, F（000） = 2272, μ = 0.498 mm-1, the final R = 0.0912 and w R = 0.1706 for 3287 observed reflections（I 〉 2σ（I））. In mono-nuclear complexes 1 and 2, the Ag（I） atom is chelated by DPEphos and dppe ligand. In the 31 P NMR spectra, there are splitting signals（doublets or triplets） which can be attributed to the coupling of the 107,109Ag–31P（from DPEphos or dppe ligand）. All the emission peaks of these complexes are attributed to ligand-centered（π-π＊） transitions.
