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

Abstract

Seven novel porous metal-organic frameworks (MOFs), Zn 2 (BTC)(NO 3 )(DMA) 3 (1), Zn 11 (BTC) 6 (NO 3 ) 4 (DEE) 9 (2), Zn 11 (BTC) 6 (NO 3 ) 4 (DEP) 8 (3), Zn(BTC)?DMA?C 2 H 8 N (4), Zn 3 (BTC) 3 ?3(C 2 H 8 N)?4(DMA) (5), Zn 9 (BTC) 6 (OH) 2 ?2(C 2 H 8 N)?15(DEE) (6), and Zn 9 (BTC) 5 (OH) 3 (C 2 O 4 )?2(C 4 H 12 N)?5(DEE) (7) have been solvothermally synthesized using zinc nitrate, 1,3,5-benzenetricarboxylate acid (H 3 BTC) 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 A ˚to 23 A ˚along with different structures: three frameworks have cages larger than 16 A ˚, one has a 23 A ˚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 NH 4 + ions.

A supermolecular building approach for the design and construction of metal–organic frameworks

“…Interestingly, Yuan et al simultaneously reported a zinctrimesate, where the trigonal MBB is now substituted by another 3-c paddlewheel. 94 Of course, there is no doubt this type of structure (beta-rht-MOFs) can be expanded by increasing the size of the branches between the 3-c central core (organic or 3-c paddlewheel) and the rdo cage, similar to what Eddaoudi et al reported for the classical ''alpha'' rht-MOFs. 12 Interestingly, the occurrence of the first beta-rht-MOF can be retroactively traced back to 2001 for a (3,3,4)-c structure reported by Zaworotko et al 95 It is not surprising that the beta-rht-MOF was not recognized back then, as the SBB approach to describe and construct MOFs, a more elaborate tool permitting to recognize net-cBUs, was not introduced until years later in 2007.…”

Size‐ and Shape‐Controlled Synthesis of Hexagonal Bipyramidal Crystals and Hollow Self‐Assembled Al‐MOF Spheres

“…However, the sizeand shape-controlled synthesis of MOFs has remained largely unexplored. Although a few reports have recently been published, [17][18][19][20][21][22][23][24][25][26] an effective level of control over particle size and shape has not yet been accomplished.…”

Crystal structure of poly[bis(ammonium) [bis(μ4-benzene-1,3,5-tricarboxylato)dizincate] 1-methylpyrrolidin-2-one disolvate]

“…ISSN 2056-9890 In our recent work (Ordonez et al, 2014), we reported 13 different Zn-BTC coordination networks that were formed as a result of the use of different cations as framework templates. Generally, only one type of secondary building unit (SBU) is observed in one compound; however, data from our and other groups (Ordonez et al, 2014;Xie, 2013;Hao et al, 2012) have shown the possibility of different SBUs in a single selfassembled system which can, in turn, result in distinct frameworks and topologies. In some cases, hydrothermal reaction conditions lead to decomposition of solvents or bases (Burrows et al, 2005), and fixation of the decomposition products in the systems can result in unexpected guests such as ammonium cations (Ordonez et al, 2014).…”