Jump to main content
Jump to site search


Flexibility in Metal-Organic Frameworks Derived from Positional and Electronic Effects of Functional Groups

Abstract

The position of identical functional groups and the subsequent electronic density of the structural benzene rings in a zinc-based metal-organic framework (MOF) have been controlled to reveal flexibility (or breathing behavior) differences. Both ortho- and para-positioned bi-functional benzene-1,4-dicarboxylic acids (BDCs) ligands were synthesized with amino-, chloro-, methoxy-, and nitro groups. Additionally, two tri-functionalized, dimethoxy-amino and dimethoxy-nitro BDCs were prepared. All bi- and tri-functionalized BDCs were successfully incorporated into dabco MOFs (DMOFs), except two diamino BDCs which were insoluble and thermally unstable. Among the eight bi-/tri-functionalized DMOFs, only para-dimethoxy exhibited flexibility in it’s framework after evacuation in preparation for a N2 isotherm measurement. Since the dimethoxy combination has the most electron-rich environment in the benzene ring of the BDC in this series, this indicates that the electron density plays a role in the flexibility changes of identically bi-functionalized DMOFs. However, the electron density alone could not fully explain the flexibility changes suggesting that the position of the functional groups is also important. These findings have been corroborated through the synthesis of two tri-functionalized DMOFs with identical functional group locations but opposite electronic environments.

Back to tab navigation

Supplementary files

Publication details

The article was received on 21 May 2017, accepted on 10 Aug 2017 and first published on 11 Aug 2017


Article type: Paper
DOI: 10.1039/C7CE00971B
Citation: CrystEngComm, 2017, Accepted Manuscript
  •   Request permissions

    Flexibility in Metal-Organic Frameworks Derived from Positional and Electronic Effects of Functional Groups

    H. Ha, H. Hahm, D. G. Jwa, K. Yoo, M. H. Park, M. Yoon, Y. Kim and M. Kim, CrystEngComm, 2017, Accepted Manuscript , DOI: 10.1039/C7CE00971B

Search articles by author

Spotlight

Advertisements