Remarkable solvent-size effects in constructing novel porous 1,3,5-benzenetricarboxylate metal-organic frameworks
Remarkable solvent-size effects in constructing novel porous 1,3,5-benzenetricarboxylate metal-organic frameworks
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DOI：
10.1039/c2ce25343g
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发表时间：
2012-01-01
期刊：
影响因子：
3.1
通讯作者：
Yuan, Gang
中科院分区：
文献类型：
--
作者：
Hao, Xiang-Rong;Wang, Xin-Long;Yuan, Gang
七种新型多孔金属有机框架（MOF），Zn-2（BTC）（NO3）（DMA）（3）（1），Zn-11（BTC）（6）（NO3）（4）（DEE）（9）（2），Zn-11（BTC）（6）（NO3）（4）（DEP）（8）（3），Zn（BTC）中心点DMA中心点C2H8N（4）， Zn-3(BTC)(3)中心点(3)(C2H8N)中心点4(DMA)(5)、Zn-9(BTC)(6)(OH)(2)中心点2(C2H8N)中心点15(DEE)(6)和Zn-9(BTC)(5)(OH)(3)(C2O4)中心点2(C4H12N)中心点5(DEE) (7) 使用硝酸锌、1,3,5-苯三甲酸 (H3BTC) 和不同尺寸的溶剂（DMF、DMA、DEE、DEP、DPE、DPP）进行溶剂热合成，表明溶剂尺寸不仅可以显着影响孔径，而且还可以实现以前在 MOF 中未实现的新结构和拓扑。随着溶剂尺寸的增加，MOFs的孔径相应地从9埃变化到23埃，并具有不同的结构：三个框架具有大于16埃的笼子，一个具有23埃的手性笼子，五个是阴离子框架，三个具有迄今为止MOFs中未报道的拓扑结构，并且所有结构都是非互穿的。 HNMR分析估计的离子交换实验表明，5中的二甲胺离子可以与NH4+离子进行交换。
Seven novel porous metal-organic frameworks (MOFs), Zn-2(BTC)(NO3)(DMA)(3) (1), Zn-11(BTC)(6)(NO3)(4)(DEE)(9) (2), Zn-11(BTC)(6)(NO3)(4)(DEP)(8) (3), Zn(BTC)center dot DMA center dot C2H8N (4), Zn-3(BTC)(3)center dot(3)(C2H8N)center dot 4(DMA) (5), Zn-9(BTC)(6)(OH)(2)center dot 2(C2H8N)center dot 15(DEE) (6), and Zn-9(BTC)(5)(OH)(3)(C2O4)center dot 2(C4H12N)center dot 5(DEE) (7) have been solvothermally synthesized using zinc nitrate, 1,3,5-benzenetricarboxylate acid (H3BTC) and differently sized solvents (DMF, DMA, DEE, DEP, DPE, DPP), showing that the solvent size can not only dramatically influence the pore size, but also allow access to new structures and topologies previously unrealized in MOFs. With increasing solvent size, the pore size of MOFs correspondingly changes from 9 angstrom to 23 angstrom along with different structures: three frameworks have cages larger than 16 angstrom, one has a 23 angstrom chiral cage, five are anionic frameworks, three have topologies heretofore unreported in MOFs and all structures are noninterpenetrating. The ion-exchange experiment estimated by HNMR analyses shows that dimethylamine ions in 5 can be exchanged by NH4+ ions.