The theoretical simulation and verified experiments on metal separation in a Sb^3＋-OH^--Cl^-complexation-precipitation system involving hydrolysis-precipitation reactions of SbOCl, Sb4O5Cl2and Sb2O3were carried out. ...The theoretical simulation and verified experiments on metal separation in a Sb^3＋-OH^--Cl^-complexation-precipitation system involving hydrolysis-precipitation reactions of SbOCl, Sb4O5Cl2and Sb2O3were carried out. The equilibrium concentration of [Sb^3＋]Twas obtained by calculation and verified by experiments. The precipitates SbOCl,Sb4O5Cl2and Sb2O3were analyzed through the equilibrium concentration of Sb^3＋in the solution and the ΔrGΘmof transformation reactions of these materials. It is found that the concentration of [Sb^3＋]Tin verified experiments was larger than the theoretical value, where the theoretical minimum concentration of [Sb^3＋]Twas 10^-10.92mol/L at pH value of 4.6 and the minimum concentration obtained from the verified experiment was about 10^-3.8mol/L at pH value of 5.1. Different precipitates can be obtained atcertain pH. The SbOCl cannot be obtained both in theoretic calculations and in verified experiments, while the Sb8O11Cl2-H2O was generated in the experiment.展开更多
Two new hybrid chloroantimonates,namely,[Prmim]_(3)SbCl_(6)(1,Prmim=1-propyl-3-methylimidazolium)and[Hmim]_(3)SbCl_(6)(2,Hmim=1-hexyl-3-methylimidazolium),were synthesized in ionic liquids(ILs)with the yields of 97%an...Two new hybrid chloroantimonates,namely,[Prmim]_(3)SbCl_(6)(1,Prmim=1-propyl-3-methylimidazolium)and[Hmim]_(3)SbCl_(6)(2,Hmim=1-hexyl-3-methylimidazolium),were synthesized in ionic liquids(ILs)with the yields of 97%and 72%,respectively.Single-crystal X-ray diffraction(SCXRD)study reveals that 1 crystallizes in monoclinic,space group Pn with a=15.2988(12),b=13.6388(10),c=15.6761(13)A,β=98.677(7)°,V=3233.5(4)A^(3),Z=4,D_(c)=1.459 g·cm^(-3),F(000)=1440,μ=1.370 mm^(-1),R=0.0589 and wR=0.1366(I>2σ(I));2 crystallizes in the hexagonal space group of P63 with a=27.7471(6),b=27.7471(6),c=8.9811(2)A,V=5988.2(3)A^(3),Z=6,D_(c)=1.391 g·cm^(-3),F(000)=2592,μ=1.121 mm^(-1),R=0.0420 and wR=0.0726(I>2σ(I)).The photophysical properties of the title compounds were studied by solid-state optical absorption,photoluminescent excitation/emission(PLE/PL),PL decay spectra and photoluminescent quantum yield(PLQY).1 and 2 exhibit PL peaks at 627 and 607 nm,Stokes shifts of 257 and 242 nm,and PLQY of 32.5%and 49.2%,respectively.The distinct photo physical characteristics of 1 and 2 are highly related to the distortion extent of the[SbCl_(6)]^(3-)unit.展开更多
Allyl and benzyl selenides were synthesized via reactions of allyl and benzyl bromides and diselenides promoted by Sm/Sb-Cl3 system in aqueous media in moderate to good yields.
基金Project(51474257)supported by the National Natural Science Foundation of China
文摘The theoretical simulation and verified experiments on metal separation in a Sb^3＋-OH^--Cl^-complexation-precipitation system involving hydrolysis-precipitation reactions of SbOCl, Sb4O5Cl2and Sb2O3were carried out. The equilibrium concentration of [Sb^3＋]Twas obtained by calculation and verified by experiments. The precipitates SbOCl,Sb4O5Cl2and Sb2O3were analyzed through the equilibrium concentration of Sb^3＋in the solution and the ΔrGΘmof transformation reactions of these materials. It is found that the concentration of [Sb^3＋]Tin verified experiments was larger than the theoretical value, where the theoretical minimum concentration of [Sb^3＋]Twas 10^-10.92mol/L at pH value of 4.6 and the minimum concentration obtained from the verified experiment was about 10^-3.8mol/L at pH value of 5.1. Different precipitates can be obtained atcertain pH. The SbOCl cannot be obtained both in theoretic calculations and in verified experiments, while the Sb8O11Cl2-H2O was generated in the experiment.
基金the National Natural Science Foundation of China(No.21671187)the Natural Science Foundation of Fujian Province(No.2020J01118)。
文摘Two new hybrid chloroantimonates,namely,[Prmim]_(3)SbCl_(6)(1,Prmim=1-propyl-3-methylimidazolium)and[Hmim]_(3)SbCl_(6)(2,Hmim=1-hexyl-3-methylimidazolium),were synthesized in ionic liquids(ILs)with the yields of 97%and 72%,respectively.Single-crystal X-ray diffraction(SCXRD)study reveals that 1 crystallizes in monoclinic,space group Pn with a=15.2988(12),b=13.6388(10),c=15.6761(13)A,β=98.677(7)°,V=3233.5(4)A^(3),Z=4,D_(c)=1.459 g·cm^(-3),F(000)=1440,μ=1.370 mm^(-1),R=0.0589 and wR=0.1366(I>2σ(I));2 crystallizes in the hexagonal space group of P63 with a=27.7471(6),b=27.7471(6),c=8.9811(2)A,V=5988.2(3)A^(3),Z=6,D_(c)=1.391 g·cm^(-3),F(000)=2592,μ=1.121 mm^(-1),R=0.0420 and wR=0.0726(I>2σ(I)).The photophysical properties of the title compounds were studied by solid-state optical absorption,photoluminescent excitation/emission(PLE/PL),PL decay spectra and photoluminescent quantum yield(PLQY).1 and 2 exhibit PL peaks at 627 and 607 nm,Stokes shifts of 257 and 242 nm,and PLQY of 32.5%and 49.2%,respectively.The distinct photo physical characteristics of 1 and 2 are highly related to the distortion extent of the[SbCl_(6)]^(3-)unit.
基金Project supported by the National Natural Science Foundation of China (Nos.29872010 and 294938004), the Natural Science Foundation of Zhejiang Province and the Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Acade
文摘Allyl and benzyl selenides were synthesized via reactions of allyl and benzyl bromides and diselenides promoted by Sm/Sb-Cl3 system in aqueous media in moderate to good yields.
