Interpenetration control, sorption behavior, and framework flexibility in Zn(II) metal-organic frameworks

Ji Hye Park, Woo Ram Lee, Yeonga Kim, Hye Jin Lee, Dae Won Ryu, Won Ju Phang, Chang Seop Hong

Research output: Contribution to journalArticlepeer-review

40 Citations (Scopus)

Abstract

Three Zn(II) frameworks [Zn(H2L)(bdc)]·1.4DEF·0. 6H2O (1; H2L = 1,4-di(1H-imidazol-4-yl)benzene, H 2bdc = terephthalic acid), [Zn(H2L)(bdc)]·1. 5DMF·1.2H2O (2), and [Zn(H2L)(L) 0.5(bdc)0.5]·formamide·H2O (3) were prepared under the solvothermal conditions in DEF/H2O, DMF/H2O, and formamide/H2O solvent pairs, respectively. All compounds are commonly based on the adamantanoid three-dimensional networks that are mutually entangled to form a 3-fold (1) to 4-fold (2) to 5-fold interpenetrating dia structure (3). The solvent pairs used in the reactions are primarily responsible for the variation of such interpenetration degree. It is noted that the reaction time, temperature, and reactant ratio applied in the present system (2) did not lead to the interpenetration change. The activated sample (1a) shows the gas uptake of N2, H2, and CO 2, characteristic of permanent porosity in the flexible framework, while the gases of N2 and H2 are not adsorbed on 2 and 3. The porous compound (1) also exhibits the reversible inclusion and release of I2 in MeOH. Interestingly, 2 reveals the reversible structural transformation during the activation-resolvation process where the solid can be activated through two routes (solvent exchange/desolvation and direct desolvation). However, there is no appreciable structural flexibility upon solvent exchange in 3 with 5-fold interpenetration, indicating that this framework is more robust, compared to 1 and 2 with lower interpenetration degrees.

Original languageEnglish
Pages (from-to)699-704
Number of pages6
JournalCrystal Growth and Design
Volume14
Issue number2
DOIs
Publication statusPublished - 2014 Feb 5

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

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