Issue 17, 2012

Remarkable solvent-size effects in constructing novel porous 1,3,5-benzenetricarboxylate metal–organic frameworks

Abstract

Seven novel porous metal–organic frameworks (MOFs), Zn2(BTC)(NO3)(DMA)3 (1), Zn11(BTC)6(NO3)4(DEE)9 (2), Zn11(BTC)6(NO3)4(DEP)8 (3), Zn(BTC)·DMA·C2H8N (4), Zn3(BTC)3·3(C2H8N)·4(DMA) (5), Zn9(BTC)6(OH)2·2(C2H8N)·15(DEE) (6), and Zn9(BTC)5(OH)3(C2O4)·2(C4H12N)·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 Å to 23 Å along with different structures: three frameworks have cages larger than 16 Å, one has a 23 Å 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.

Graphical abstract: Remarkable solvent-size effects in constructing novel porous 1,3,5-benzenetricarboxylate metal–organic frameworks

Supplementary files

Article information

Article type
Paper
Submitted
09 Mar 2012
Accepted
11 May 2012
First published
14 May 2012

CrystEngComm, 2012,14, 5596-5603

Remarkable solvent-size effects in constructing novel porous 1,3,5-benzenetricarboxylate metal–organic frameworks

X. Hao, X. Wang, K. Shao, G. Yang, Z. Su and G. Yuan, CrystEngComm, 2012, 14, 5596 DOI: 10.1039/C2CE25343G

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