Cyclic Structural Transformations from Crystalline to Crystalline to Amorphous Phases and Magnetic Properties of a Mn(II)-Based Metal-Organic Framework

Han Geul Lee, Hyuna Jo, Sunhwi Eom, Dong Won Kang, Minjung Kang, Jeremy Hilgar, Jeffrey D. Rinehart, Dohyun Moon, Chang Seop Hong

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

A three-dimensional Mn(II) framework, [Mn2(H2L)(L)0.5(MeOH)(DEF)]·0.1MeOH·0.1DEF·1.4H2O (1; H4L = 2,3-dioxido-1,4-benzenedicarboxylic acid), was synthesized under solvothermal conditions in diethylformamide/methanol (DEF/MeOH), where the Mn centers adopt octahedral and unusual pentagonal bipyramidal geometries. The ligand H4L was subject to deprotonation to create μ4-H2L2- and μ6-L4- anionic bridges, leading to the construction of a coordination network. The MeOH exchange process of crystalline 1 allowed for another crystalline phase (1a), which reversibly returned to the original crystalline state upon resolvation in DEF/MeOH. After evacuation of 1a, the amorphous phase 1b was irreversibly formed, followed by the restoration of the original phase 1 upon resolvation in DEF/MeOH. Consequently, this framework underwent cyclic structural transformations from the crystalline (1) to crystalline (1a) to amorphous (1b) and back to crystalline (1) phase, which are unique transformations for soft coordination networks. Magnetic measurements demonstrated that antiferromagnetic interactions were operative between the Mn(II) ions and were effectively mediated by the oxygen moieties of the μ6-L4- bridge.

Original languageEnglish
Pages (from-to)3360-3365
Number of pages6
JournalCrystal Growth and Design
Volume18
Issue number6
DOIs
Publication statusPublished - 2018 Jun 6

ASJC Scopus subject areas

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

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