Pillared-bilayer zinc(ii)-organic laminae: pore modification and selective gas adsorption

Li Wei Lee, Tzuoo Tsair Luo, Sheng Han Lo, Gene Hsiang Lee, Shie Ming Peng, Yen Hsiang Liu, Sheng Long Lee, Kuang Lieh Lu

Research output: Contribution to journalArticlepeer-review

12 Scopus citations

Abstract

Three porous metal-organic frameworks, namely {[Zn2(azpy)(aip)2]·2DMF}n (1, azpy = 4,4′-azobipyridine, H2aip = 5-aminoisophthalic acid), {[Zn2(dipytz)(aip)2]·1.15DMF·0.85MeOH}n (2, dipytz = di-3,6-(4-pyridyl)-1,2,4,5-tetrazine) and {[Zn2(tpim)(aip)2]·2.5DMF·2H2O}n (3, tpim = 2,4,5-tri(4-pyridyl)imidazole), were synthesized under mild conditions. All of the compounds consisted of a honeycomb-like layer, [Zn(aip)]n, further pillared by N-donor ligands to form two-dimensional (2D) porous pillared-bilayer frameworks with 1D channels created inside the bilayers (4.1 × 10.1 Å2 for 1, 4.1 × 11.1 Å2 for 2, and 5.1 × 9.8 Å2 for 3). The resulting MOFs showed different pore volumes and channel shapes depending on the length and shape of the pillar ligands (35.7%, 41.7%, and 33.9% for 1-3, respectively). The pore volume in 3 decreased due to the presence of the uncoordinated pyridyl group of the tpim ligand. The frameworks of 1 and 2 show flexible properties upon undergoing solvent-exchange processes and their CO2 adsorption properties are different. These latter properties are affected by the functional groups of the linear pillar ligand (-N=N- and tetrazine group). In particular, compound 3 possesses less flexibility upon undergoing a solvent-exchange process and preferentially absorbs CO2 more efficiently rather than H2 and N2.

Original languageEnglish
Pages (from-to)6320-6327
Number of pages8
JournalCrystEngComm
Volume17
Issue number33
DOIs
StatePublished - 9 Jul 2015

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