A natural mineral, lindgrenite Cu3 （ MoO4 ）2 （ OH）2, was synthesized from a mixture of sodium molybdate, copper sulfate, and morpholine in water under autogenous pressure at 170 ℃. The crystal structure of the mi...A natural mineral, lindgrenite Cu3 （ MoO4 ）2 （ OH）2, was synthesized from a mixture of sodium molybdate, copper sulfate, and morpholine in water under autogenous pressure at 170 ℃. The crystal structure of the mineral was determined and the final refinement for 791 observed reflections with Ⅰ 〉 2σ（Ⅰ） gave R1 = 0. 0205 and wR2 = 0. 0496. The thermal stability of the mineral was investigated by using TG-DTA and variable-temperature in situ X-ray diffraction（XRD） techniques. The crystalline Cu3Mo2O9 was obtained when the mineral underwent thermal dehydration at a temperature ranging from 300 to 400 ℃, and the mixture of MoO3 and CuO was formed through decomposition of Cu3Mo2O9 at a temperature ranging from 650 to 700 ℃. Therefore, the structure of the mineral was thermally unstable at above 300 ℃, suggesting that Lindgrenite was likely formed via the hydrothermal route occurring in the nature.展开更多
Reaction of SmI2（THF）x with 2 equivalents of NaOAr （Ar = C6H2-tert-Bu3-2,4,6） in THF affords a divalent complex of Sm（OAr）2（THF）yTHF 1 in 90.8% yield. Treatment of 1 with 1,2-dimethoxyethane （DME） leads to t...Reaction of SmI2（THF）x with 2 equivalents of NaOAr （Ar = C6H2-tert-Bu3-2,4,6） in THF affords a divalent complex of Sm（OAr）2（THF）yTHF 1 in 90.8% yield. Treatment of 1 with 1,2-dimethoxyethane （DME） leads to the ligand-exchange reaction, and a DME-solvated complex of Sm（OAr）2（DME）2 2 was obtained. Complex 1 crystallizes in monoclinic, space group P21/c with a = 10.366（5）, b = 33.024（15）, c = 16.123（7） A, β = 93.197（8）°, V = 5511 （4） A^3, Z = 4, C52H90O6Sm, Mr = 961.59, Dc = 1.159 g/cm^3, F（000） = 2048,μ（MoKα） = 1.107 mm^-1, R = 0.0844 and wR = 0.1401 for 4694 observed reflections. Complex 2 crystallizes in monoclinic, space group C2/c with a = 27.222（5）, b = 10.6140（19）, c = 17.398（4） A, β = 110.245（3）°, V = 4716.4（16） A^3, Z = 4, C44H78O6Sm, Mr = 853.41, Dc = 1.202 g/cm^3, F（000） = 1808,μ（MoKα） = 1.285 mm^-1, R = 0.0361 and wR = 0.0830 for 5210 observed reflections.展开更多
Three zinc(Ⅱ) metal-organic frameworks (x F-MAC-3) have been synthesized by using Zn(Ⅱ) salts,3,5-dimethyl-1H-1,2,4-triazole (Hdmtrz) and different fluorination degree carboxylate ligands,which are analogic structur...Three zinc(Ⅱ) metal-organic frameworks (x F-MAC-3) have been synthesized by using Zn(Ⅱ) salts,3,5-dimethyl-1H-1,2,4-triazole (Hdmtrz) and different fluorination degree carboxylate ligands,which are analogic structures and can be described as (6,6)-connected pcu-b net.We find that the fluorine atoms have structural regulation effect on x F-MAC-3,which can not only enlarge the torsion angle φ of carboxylate ligands but also elevate the space group of structures.Besides,the CO_(2)-273 K uptake increased from 23.21 cm^(3)·g^(-1) (MAC-3) to36.13 cm^(3)·g^(-1) (4F-MAC-3) and H_(2)-77 K uptake increased from 24.33 cm^(3)·g^(-1) (MAC-3) to 59.79 cm^(3)·g^(-1)(4F-MAC-3),which means fluorination can enhance the gas adsorption uptake of x F-MAC-3 analogues.Furthermore,the results of fluorination in x F-MAC-3 analogues offer a potential way to study the ligand pre-functionalization effect on the structures and properties of MOFs analogues.展开更多
基金Supported by the National Natural Science Foundation of China(No. 20371013, 20421303),National Key Basic ResearchProgram of China(No. 2003CB615807) the State Key Laboratory Base of Novel Functional Materials and Preparation Science(Ningbo University).
文摘A natural mineral, lindgrenite Cu3 （ MoO4 ）2 （ OH）2, was synthesized from a mixture of sodium molybdate, copper sulfate, and morpholine in water under autogenous pressure at 170 ℃. The crystal structure of the mineral was determined and the final refinement for 791 observed reflections with Ⅰ 〉 2σ（Ⅰ） gave R1 = 0. 0205 and wR2 = 0. 0496. The thermal stability of the mineral was investigated by using TG-DTA and variable-temperature in situ X-ray diffraction（XRD） techniques. The crystalline Cu3Mo2O9 was obtained when the mineral underwent thermal dehydration at a temperature ranging from 300 to 400 ℃, and the mixture of MoO3 and CuO was formed through decomposition of Cu3Mo2O9 at a temperature ranging from 650 to 700 ℃. Therefore, the structure of the mineral was thermally unstable at above 300 ℃, suggesting that Lindgrenite was likely formed via the hydrothermal route occurring in the nature.
基金The project was supported by the Qinglan Foundation of Jiangsu Province (HB2001-27) and the Foundation of Educational Commission of Jiangsu Province (04KJD560171)
文摘Reaction of SmI2（THF）x with 2 equivalents of NaOAr （Ar = C6H2-tert-Bu3-2,4,6） in THF affords a divalent complex of Sm（OAr）2（THF）yTHF 1 in 90.8% yield. Treatment of 1 with 1,2-dimethoxyethane （DME） leads to the ligand-exchange reaction, and a DME-solvated complex of Sm（OAr）2（DME）2 2 was obtained. Complex 1 crystallizes in monoclinic, space group P21/c with a = 10.366（5）, b = 33.024（15）, c = 16.123（7） A, β = 93.197（8）°, V = 5511 （4） A^3, Z = 4, C52H90O6Sm, Mr = 961.59, Dc = 1.159 g/cm^3, F（000） = 2048,μ（MoKα） = 1.107 mm^-1, R = 0.0844 and wR = 0.1401 for 4694 observed reflections. Complex 2 crystallizes in monoclinic, space group C2/c with a = 27.222（5）, b = 10.6140（19）, c = 17.398（4） A, β = 110.245（3）°, V = 4716.4（16） A^3, Z = 4, C44H78O6Sm, Mr = 853.41, Dc = 1.202 g/cm^3, F（000） = 1808,μ（MoKα） = 1.285 mm^-1, R = 0.0361 and wR = 0.0830 for 5210 observed reflections.
基金supported by the NSFC (No. 21971045)Natural Science Foundation of Shanghai (No. 18ZR1402900)+1 种基金the National Key Technologies R&D Program of China (2017YFA0205103)Shanghai Leading Academic Discipline Project (B108)。
文摘Three zinc(Ⅱ) metal-organic frameworks (x F-MAC-3) have been synthesized by using Zn(Ⅱ) salts,3,5-dimethyl-1H-1,2,4-triazole (Hdmtrz) and different fluorination degree carboxylate ligands,which are analogic structures and can be described as (6,6)-connected pcu-b net.We find that the fluorine atoms have structural regulation effect on x F-MAC-3,which can not only enlarge the torsion angle φ of carboxylate ligands but also elevate the space group of structures.Besides,the CO_(2)-273 K uptake increased from 23.21 cm^(3)·g^(-1) (MAC-3) to36.13 cm^(3)·g^(-1) (4F-MAC-3) and H_(2)-77 K uptake increased from 24.33 cm^(3)·g^(-1) (MAC-3) to 59.79 cm^(3)·g^(-1)(4F-MAC-3),which means fluorination can enhance the gas adsorption uptake of x F-MAC-3 analogues.Furthermore,the results of fluorination in x F-MAC-3 analogues offer a potential way to study the ligand pre-functionalization effect on the structures and properties of MOFs analogues.
