Four C_1-symmetric ansa-metallocene complexes, C_2H_4(Ind)(2,7-~tBu_2-Flu)ZrCl_2(4), C_2H_4(3-Bn-Ind)(2,7-~tBu_2-Flu)ZrCl_2(5),C_2H_4(3-Bn-Ind)(3,6-~tBu_2-Flu)ZrCl_2(6), and C_2H_4(3-Bn-Ind)(2,7-~tBu_2-Flu)HfCl_2(7), ...Four C_1-symmetric ansa-metallocene complexes, C_2H_4(Ind)(2,7-~tBu_2-Flu)ZrCl_2(4), C_2H_4(3-Bn-Ind)(2,7-~tBu_2-Flu)ZrCl_2(5),C_2H_4(3-Bn-Ind)(3,6-~tBu_2-Flu)ZrCl_2(6), and C_2H_4(3-Bn-Ind)(2,7-~tBu_2-Flu)HfCl_2(7), were synthesized and characterized. The structures of complexes 4, 5, and 7 were further determined via X-ray diffraction studies. Upon activation with modified methylaluminoxane(MMAO) or Al^iBu_3/[Ph_3C][B(C_6F_5)_4](TIBA/TrB), most of these complexes showed high efficiency in catalyzing propylene oligomerization/polymerization to afford products dominantly with allyl terminals via selective β-methyl transfer(β-Me transfer). The introduction of 3-benzyl group on the indenyl ring of the complexes was found to be crucial in enabling highly selective β-Me transfer during the polymerization process, leading to selectivities up to 89% obtained by zirconocene complexes 5 and 6, and up to 91% obtained by hafnocene complex 7. Detailed chain-end analysis by ~1H-NMR, ^(13)C-NMR, and MALDI-TOF mass spectroscopy revealed that the allyl chain-ends of the polymeric products resulted from a selective β-Me transfer process after two successively primary insertions of the monomer. Further studies concerning the dependence of chain release selectivity as well as the molecular weight of products on monomer concentration suggested that both β-Me transfer(major) and β-hydrogen transfer(β-H transfer)(minor) mediated by 5/MMAO and 6/MMAO systems may mainly operate in a bimolecular pathway.展开更多
Three novel triarylamine dyes（AFL1-AFL3） containing fluorenyl and the biphenyl moieties have been designed and synthesized for application in dye-sensitized solar cells.The light-harvesting capabilities and photovol...Three novel triarylamine dyes（AFL1-AFL3） containing fluorenyl and the biphenyl moieties have been designed and synthesized for application in dye-sensitized solar cells.The light-harvesting capabilities and photovoltaic performance of these dyes were investigated systematically through comparison of different π-bridges.The dye with a furan linker exhibited a higher open-circuit voltage（VOC） and monochromatic incident photon-to-current conversion efficiency（IPCE） compared to thiophene and benzene linker.Thus,AFL3 containing a furan linker exhibited the maximum overall conversion efficiency of 5.81%（VOC = 760 mV,JSC = 11.36 mA cm^-2 and ff=0.68） under standard global AM 1.5 G solar condition.展开更多
In the field of highly integrated printed circuit board （PCB）, the heat resistant substrate with low water absorption is very important material. To get the resin composition for the high functional substrate materi...In the field of highly integrated printed circuit board （PCB）, the heat resistant substrate with low water absorption is very important material. To get the resin composition for the high functional substrate material with low moisture absorption and high glass transition temperature （Tg） simultaneously, a fluorenyl ＂Cardo＂ epoxy was incorporated into novolac cyanate ester resin. As an optimum curing agent for the fiuorenyl epoxy, methyl nadic anhydride （MNA） was selected. Silica powders as fillers were added into the resin composition. The partial replacement of the cyanate ester resin with the fluorenyl epoxy could reduce the moisture absorption with keeping high glass transition temperature over 300 ℃. The laminate, which was fabricated from prepregs made with 40 wt% silica-filled resin composition and glass fabric, showed high Tg of 317 ℃ and low moisture absorption of 0.57%.展开更多
Comprehensive Summary Open-shell graphene fragments(OGFs)with non-benzenoid topologies are attracting increasing attention due to their potential applications in organic light-emitting diodes(OLEDs)and organic radical...Comprehensive Summary Open-shell graphene fragments(OGFs)with non-benzenoid topologies are attracting increasing attention due to their potential applications in organic light-emitting diodes(OLEDs)and organic radical conductors.Herein,we report the synthesis of an air-stable fluorenyl radical derivative(AR1)containing a seven-membered ring,achieving thermodynamic stabilization through the fusion of a naphthalene ring around its periphery and anthracene substituent.展开更多
Comprehensive Summary A design strategy towards stable fluorenyl radicals(FRs)has been developed through introducing donor-π-radical(D-π-R)conjugation,facilitated by the linkage of amine N atoms and FR centers via p...Comprehensive Summary A design strategy towards stable fluorenyl radicals(FRs)has been developed through introducing donor-π-radical(D-π-R)conjugation,facilitated by the linkage of amine N atoms and FR centers via phenyl or 9-anthryl moieties.Four FRs,with or without N atom containing protecting groups,were designed and synthesized for comparative analysis.展开更多
A new fluorescent sensor consisted of fluorenyl and dioxotetraaza unit, dimethyl-6-(9-fluorenyl)-1,4,8,11-tetraazaundencane-5,7-dione (L), was synthesize fluorescent sensor for transition metal ions in aqueous solution.
基金financially supported by the National Natural Science Foundation of China (No. 21274041)the Key Project of Chinese Ministry of Education (No. 109064)the Fundamental Research Funds for the Central Universities (No. WK1214048)
文摘Four C_1-symmetric ansa-metallocene complexes, C_2H_4(Ind)(2,7-~tBu_2-Flu)ZrCl_2(4), C_2H_4(3-Bn-Ind)(2,7-~tBu_2-Flu)ZrCl_2(5),C_2H_4(3-Bn-Ind)(3,6-~tBu_2-Flu)ZrCl_2(6), and C_2H_4(3-Bn-Ind)(2,7-~tBu_2-Flu)HfCl_2(7), were synthesized and characterized. The structures of complexes 4, 5, and 7 were further determined via X-ray diffraction studies. Upon activation with modified methylaluminoxane(MMAO) or Al^iBu_3/[Ph_3C][B(C_6F_5)_4](TIBA/TrB), most of these complexes showed high efficiency in catalyzing propylene oligomerization/polymerization to afford products dominantly with allyl terminals via selective β-methyl transfer(β-Me transfer). The introduction of 3-benzyl group on the indenyl ring of the complexes was found to be crucial in enabling highly selective β-Me transfer during the polymerization process, leading to selectivities up to 89% obtained by zirconocene complexes 5 and 6, and up to 91% obtained by hafnocene complex 7. Detailed chain-end analysis by ~1H-NMR, ^(13)C-NMR, and MALDI-TOF mass spectroscopy revealed that the allyl chain-ends of the polymeric products resulted from a selective β-Me transfer process after two successively primary insertions of the monomer. Further studies concerning the dependence of chain release selectivity as well as the molecular weight of products on monomer concentration suggested that both β-Me transfer(major) and β-hydrogen transfer(β-H transfer)(minor) mediated by 5/MMAO and 6/MMAO systems may mainly operate in a bimolecular pathway.
基金National Natural Science Foundation of China (No. 21176223)National Natural Science Foundation of China (No. 21406202)Natural Science Foundation of Zhejiang province (No. LY15B020009)
文摘Three novel triarylamine dyes（AFL1-AFL3） containing fluorenyl and the biphenyl moieties have been designed and synthesized for application in dye-sensitized solar cells.The light-harvesting capabilities and photovoltaic performance of these dyes were investigated systematically through comparison of different π-bridges.The dye with a furan linker exhibited a higher open-circuit voltage（VOC） and monochromatic incident photon-to-current conversion efficiency（IPCE） compared to thiophene and benzene linker.Thus,AFL3 containing a furan linker exhibited the maximum overall conversion efficiency of 5.81%（VOC = 760 mV,JSC = 11.36 mA cm^-2 and ff=0.68） under standard global AM 1.5 G solar condition.
文摘In the field of highly integrated printed circuit board （PCB）, the heat resistant substrate with low water absorption is very important material. To get the resin composition for the high functional substrate material with low moisture absorption and high glass transition temperature （Tg） simultaneously, a fluorenyl ＂Cardo＂ epoxy was incorporated into novolac cyanate ester resin. As an optimum curing agent for the fiuorenyl epoxy, methyl nadic anhydride （MNA） was selected. Silica powders as fillers were added into the resin composition. The partial replacement of the cyanate ester resin with the fluorenyl epoxy could reduce the moisture absorption with keeping high glass transition temperature over 300 ℃. The laminate, which was fabricated from prepregs made with 40 wt% silica-filled resin composition and glass fabric, showed high Tg of 317 ℃ and low moisture absorption of 0.57%.
文摘Comprehensive Summary Open-shell graphene fragments(OGFs)with non-benzenoid topologies are attracting increasing attention due to their potential applications in organic light-emitting diodes(OLEDs)and organic radical conductors.Herein,we report the synthesis of an air-stable fluorenyl radical derivative(AR1)containing a seven-membered ring,achieving thermodynamic stabilization through the fusion of a naphthalene ring around its periphery and anthracene substituent.
基金supported by Natural Science Foundation of China(22175128)starting grants of Tianjin University.
文摘Comprehensive Summary A design strategy towards stable fluorenyl radicals(FRs)has been developed through introducing donor-π-radical(D-π-R)conjugation,facilitated by the linkage of amine N atoms and FR centers via phenyl or 9-anthryl moieties.Four FRs,with or without N atom containing protecting groups,were designed and synthesized for comparative analysis.
文摘A new fluorescent sensor consisted of fluorenyl and dioxotetraaza unit, dimethyl-6-(9-fluorenyl)-1,4,8,11-tetraazaundencane-5,7-dione (L), was synthesize fluorescent sensor for transition metal ions in aqueous solution.
