A new inorganic-organic hybrid framework microporous material Cd 3(BDC) 0.5(BTC) 2·(DMF)(H 2O)·3DMF·H 3O·H 2O, in which two kinds of carboxylate ligands coordinate with cadmium ions synchronously, ...A new inorganic-organic hybrid framework microporous material Cd 3(BDC) 0.5(BTC) 2·(DMF)(H 2O)·3DMF·H 3O·H 2O, in which two kinds of carboxylate ligands coordinate with cadmium ions synchronously, was obtained under a mild synthesis condition. The titled compound is crystallized in a monoclinic system, space group P2(1)/c with a=1.584 7(7) nm, b=1.426 7(6) nm, c=1.936 3(6) nm, β=113.186(7)°, V=4.024 6(3) nm 3, Z=4, D X=1.947 mg/m 3, M r=1 179.92, μ=1.662 mm -1, F(000)=2 344, R=0.074 8, wR=0.215 1. Three cadmium centers link with each other through BDC or BTC ligand to form a 3-D open framework.展开更多
为探究溶剂对合成有机金属框架化合物的影响机制,采用实验和DFT理论计算相结合的方法,研究溶剂N,N-二甲基甲酰胺(DMF)和N-甲基-2-吡咯烷酮(NMP)对溶剂热法合成有机金属框架材料[Zn4O(BDC)3]8的影响及溶剂与框架间的微观作用机制。粉末X...为探究溶剂对合成有机金属框架化合物的影响机制,采用实验和DFT理论计算相结合的方法,研究溶剂N,N-二甲基甲酰胺(DMF)和N-甲基-2-吡咯烷酮(NMP)对溶剂热法合成有机金属框架材料[Zn4O(BDC)3]8的影响及溶剂与框架间的微观作用机制。粉末X射线衍射(XRD)和扫描电镜(SEM)结果表明,NMP在[Zn4O(BDC)3]8孔道中的吸附力较DMF的弱,NMP分子更容易从框架中脱除;热重(TG)和热重-红外联用(TGA/FT-IR)结果表明,以DMF为溶剂合成的[Zn4O(BDC)3]8的热分解温度和热稳定性较高;氮气等温吸附实验(BET)发现,以NMP为溶剂合成的[Zn4O(BDC)3]8的气体吸附性能更强,兰缪尔比表面积高于用DMF合成的[Zn4O(BDC)3]8。调控介电常数设定溶剂分别为NMP和DMF,用COSMO溶剂化方法对溶剂分子与框架化合物基本结构单元Zn4O(BDC)3间相互作用模型进行几何优化计算,发现溶剂设定为NMP时Zn4O(BDC)3优化结构的总能量较溶剂设定为DMF时的高8.6405 k J/mol,这说明DMF分子与Zn4O(BDC)3间的结合力强于NMP分子的,溶剂化作用降低了Zn与O间的离子性;用DMol3在GGA-BLYP/DN水平计算了DMF、NMP或DEF溶剂分子在[Zn4O(BDC)3]8晶体孔道中的相互作用,与DMF相比,NMP在孔道中能量状态稳定性较差,在能量状态角度上NMP应最容易从框架材料孔道中脱除。研究结果说明NMP更有利于合成性质良好的[Zn4O(BDC)3]8,与DMF相比NMP与框架结构基元间的作用力较弱。展开更多
A 3-D inorganic-organic hybrid framework microporous material [Co 3(BDC) 3(EG) 4]·2DMF was synthesized under mild conditions and its crystal structure was determined by using single crystal X-ray diffraction. The...A 3-D inorganic-organic hybrid framework microporous material [Co 3(BDC) 3(EG) 4]·2DMF was synthesized under mild conditions and its crystal structure was determined by using single crystal X-ray diffraction. The crystal structure was solved by a direct method and refined by full-matrix least-square method. The crystal is the triclinic system and belongs to space group P-1 with a=9.978(2) nm, b=11.223(2) nm, c=11.283(2) nm, α=102.26(3)°, β=113.52(3)°, γ=92.73(3)°, V=6.329(2) nm 3, Z=1, D c=1.565 Mg/m 3, M r=1 063.59, μ=1.183 mm -1, F(000)=541, GOF=1.024, R=0.044 2, wR=0.124 9.展开更多
文摘A new inorganic-organic hybrid framework microporous material Cd 3(BDC) 0.5(BTC) 2·(DMF)(H 2O)·3DMF·H 3O·H 2O, in which two kinds of carboxylate ligands coordinate with cadmium ions synchronously, was obtained under a mild synthesis condition. The titled compound is crystallized in a monoclinic system, space group P2(1)/c with a=1.584 7(7) nm, b=1.426 7(6) nm, c=1.936 3(6) nm, β=113.186(7)°, V=4.024 6(3) nm 3, Z=4, D X=1.947 mg/m 3, M r=1 179.92, μ=1.662 mm -1, F(000)=2 344, R=0.074 8, wR=0.215 1. Three cadmium centers link with each other through BDC or BTC ligand to form a 3-D open framework.
基金Project(51104185)supported by the National Natural Science Foundation of ChinaProject(2010QZZD003)supported by the Key Project of Central South University of Fundamental Research Funds for the Central Universities of China
文摘为探究溶剂对合成有机金属框架化合物的影响机制,采用实验和DFT理论计算相结合的方法,研究溶剂N,N-二甲基甲酰胺(DMF)和N-甲基-2-吡咯烷酮(NMP)对溶剂热法合成有机金属框架材料[Zn4O(BDC)3]8的影响及溶剂与框架间的微观作用机制。粉末X射线衍射(XRD)和扫描电镜(SEM)结果表明,NMP在[Zn4O(BDC)3]8孔道中的吸附力较DMF的弱,NMP分子更容易从框架中脱除;热重(TG)和热重-红外联用(TGA/FT-IR)结果表明,以DMF为溶剂合成的[Zn4O(BDC)3]8的热分解温度和热稳定性较高;氮气等温吸附实验(BET)发现,以NMP为溶剂合成的[Zn4O(BDC)3]8的气体吸附性能更强,兰缪尔比表面积高于用DMF合成的[Zn4O(BDC)3]8。调控介电常数设定溶剂分别为NMP和DMF,用COSMO溶剂化方法对溶剂分子与框架化合物基本结构单元Zn4O(BDC)3间相互作用模型进行几何优化计算,发现溶剂设定为NMP时Zn4O(BDC)3优化结构的总能量较溶剂设定为DMF时的高8.6405 k J/mol,这说明DMF分子与Zn4O(BDC)3间的结合力强于NMP分子的,溶剂化作用降低了Zn与O间的离子性;用DMol3在GGA-BLYP/DN水平计算了DMF、NMP或DEF溶剂分子在[Zn4O(BDC)3]8晶体孔道中的相互作用,与DMF相比,NMP在孔道中能量状态稳定性较差,在能量状态角度上NMP应最容易从框架材料孔道中脱除。研究结果说明NMP更有利于合成性质良好的[Zn4O(BDC)3]8,与DMF相比NMP与框架结构基元间的作用力较弱。
文摘A 3-D inorganic-organic hybrid framework microporous material [Co 3(BDC) 3(EG) 4]·2DMF was synthesized under mild conditions and its crystal structure was determined by using single crystal X-ray diffraction. The crystal structure was solved by a direct method and refined by full-matrix least-square method. The crystal is the triclinic system and belongs to space group P-1 with a=9.978(2) nm, b=11.223(2) nm, c=11.283(2) nm, α=102.26(3)°, β=113.52(3)°, γ=92.73(3)°, V=6.329(2) nm 3, Z=1, D c=1.565 Mg/m 3, M r=1 063.59, μ=1.183 mm -1, F(000)=541, GOF=1.024, R=0.044 2, wR=0.124 9.
