Anhydrous EuCl3 reacted with sodium carbon-bridged biphenolate LNa2[ L = 2,2＇-methylene bis（6-tert-butyl-4- methyl-phenoxo ] in a 1 ： 1 molar ratio in THF in the presence of HMPA （HMPA = hexamethylphosphoric triam...Anhydrous EuCl3 reacted with sodium carbon-bridged biphenolate LNa2[ L = 2,2＇-methylene bis（6-tert-butyl-4- methyl-phenoxo ] in a 1 ： 1 molar ratio in THF in the presence of HMPA （HMPA = hexamethylphosphoric triamide）, then the product formed in situ was reduced by Na-K alloy to generate the divalent carbon-bridged biphenolate europium complex [ LEu （HMPA） 2 ] 2 （THF） 4 （ 1 ） in a good isolated yield. Complex 1 was fully characterized by elemental analysis, NMR and IR spectra, and X-ray structural determination. The crystal data of complex 1 are monoclinic, P2 1/c space group, a=1.6521（3） nm, b=2.8274（3） nm, c=1.2074（2） nm, β=111.723（6）°, V=5.2393（14） nm^3, Z=2, Dc= 1.259 mg·m^-3, μ = 1.304 mm^-1, F（000） = 2092, R = 0.0815, wR = 0. 1723. Complex 1 is a dimer with two Eu - O bridges. The coordination geometry of each europium atom can be best described as a distorted trigonal bipyramid.展开更多
A novel phosphonate-based chiral metal-organic framework 1 was synthesized from C2-symmetric 1,1？-biphenol-based ligand and structurally characterized by single-crystal and powder X-ray diffraction, Fourier-transform...A novel phosphonate-based chiral metal-organic framework 1 was synthesized from C2-symmetric 1,1？-biphenol-based ligand and structurally characterized by single-crystal and powder X-ray diffraction, Fourier-transform infrared spectra（FTIR）, circular dichroism（CD） and thermogravimetric analyses（TGA）. Two neighboring Mn ions are linked by two carboxylate groups and one phosphate group to form a di-manganese unit [Mn2] and each [Mn2] cluster in 1 is linked by five ligands, generating a 3D network with fns topology. In addition, the photoluminescence properties of 1 and H4 L were investigated.展开更多
Aqueous organic flow batteries have attracted dramatic attention for stationary energy storage due to their resource sustainability and low cost. However, the current reported systems can normally be operated stably u...Aqueous organic flow batteries have attracted dramatic attention for stationary energy storage due to their resource sustainability and low cost. However, the current reported systems can normally be operated stably under a nitrogen or argon atmosphere due to their poor stability. Herein a stable airinsensitive biphenol derivative cathode, 3,30,5,50-tetramethylaminemethylene-4,40-biphenol(TABP), with high solubility(>1.5 mol L^(-1)) and redox potential(0.91 V vs. SHE) is designed and synthesized by a scalable one-step method. Paring with silicotungstic acid(SWO), an SWO/TABP flow battery shows a stable performance of zero capacity decay over 900 cycles under the air atmosphere. Further, an SWO/TABP flow battery manifests a high rate performance with an energy efficiency of 85% at a current density of60 m A cm^(-2) and a very high volumetric capacity of more than 47 Ah L^(-1). This work provides a new and practical option for next-generation practical large-scale energy storage.展开更多
An efficient electrochemical access to the non-symmetric biphenols using tri(p-bromophenyl)amine(TBPA)as a redox mediator has been developed.The electrochemical protocol features highly selective cross-coupling produc...An efficient electrochemical access to the non-symmetric biphenols using tri(p-bromophenyl)amine(TBPA)as a redox mediator has been developed.The electrochemical protocol features highly selective cross-coupling products in up to 83% yield,instead of forming homo-coupling ones.展开更多
文摘Anhydrous EuCl3 reacted with sodium carbon-bridged biphenolate LNa2[ L = 2,2＇-methylene bis（6-tert-butyl-4- methyl-phenoxo ] in a 1 ： 1 molar ratio in THF in the presence of HMPA （HMPA = hexamethylphosphoric triamide）, then the product formed in situ was reduced by Na-K alloy to generate the divalent carbon-bridged biphenolate europium complex [ LEu （HMPA） 2 ] 2 （THF） 4 （ 1 ） in a good isolated yield. Complex 1 was fully characterized by elemental analysis, NMR and IR spectra, and X-ray structural determination. The crystal data of complex 1 are monoclinic, P2 1/c space group, a=1.6521（3） nm, b=2.8274（3） nm, c=1.2074（2） nm, β=111.723（6）°, V=5.2393（14） nm^3, Z=2, Dc= 1.259 mg·m^-3, μ = 1.304 mm^-1, F（000） = 2092, R = 0.0815, wR = 0. 1723. Complex 1 is a dimer with two Eu - O bridges. The coordination geometry of each europium atom can be best described as a distorted trigonal bipyramid.
基金Supported by NSFC(No.21431004,21522104 and 21620102001)“973”Program(No.2014CB932102 and 2016YFA0203400)+1 种基金the Shanghai“Eastern Scholar”Program SSTC-14YF1401300the Key Project of Basic Research of Shanghai(17JC1403100)
文摘A novel phosphonate-based chiral metal-organic framework 1 was synthesized from C2-symmetric 1,1？-biphenol-based ligand and structurally characterized by single-crystal and powder X-ray diffraction, Fourier-transform infrared spectra（FTIR）, circular dichroism（CD） and thermogravimetric analyses（TGA）. Two neighboring Mn ions are linked by two carboxylate groups and one phosphate group to form a di-manganese unit [Mn2] and each [Mn2] cluster in 1 is linked by five ligands, generating a 3D network with fns topology. In addition, the photoluminescence properties of 1 and H4 L were investigated.
基金The authors acknowledge financial support from the National Natural Science Foundation of China(21925804,21935003)CASDOE Collaborative Project(121421KYSB20170032)+1 种基金CAS Engineering Laboratory for Electrochemical Energy Storage,Liaoning Revitalization Talents Program(XLYC1802050)China and DICP funding,China(ZZBS201707)。
文摘Aqueous organic flow batteries have attracted dramatic attention for stationary energy storage due to their resource sustainability and low cost. However, the current reported systems can normally be operated stably under a nitrogen or argon atmosphere due to their poor stability. Herein a stable airinsensitive biphenol derivative cathode, 3,30,5,50-tetramethylaminemethylene-4,40-biphenol(TABP), with high solubility(>1.5 mol L^(-1)) and redox potential(0.91 V vs. SHE) is designed and synthesized by a scalable one-step method. Paring with silicotungstic acid(SWO), an SWO/TABP flow battery shows a stable performance of zero capacity decay over 900 cycles under the air atmosphere. Further, an SWO/TABP flow battery manifests a high rate performance with an energy efficiency of 85% at a current density of60 m A cm^(-2) and a very high volumetric capacity of more than 47 Ah L^(-1). This work provides a new and practical option for next-generation practical large-scale energy storage.
基金grants from the National Key Technology R&D Program(No.2016YFD0400801)the National Natural Science Foundation of China(No.21871019).
文摘An efficient electrochemical access to the non-symmetric biphenols using tri(p-bromophenyl)amine(TBPA)as a redox mediator has been developed.The electrochemical protocol features highly selective cross-coupling products in up to 83% yield,instead of forming homo-coupling ones.
