Jump to main content
Jump to site search

Issue 13, 2018
Previous Article Next Article

Nanopore-induced host–guest charge transfer phenomena in a metal–organic framework

Author affiliations

Abstract

A spontaneous entrapment of electron-donating small guest molecules, including tetrathiafulvalene (TTF) and N,N,N′,N′-tetramethyl-1,3-propanediamine (TMPDA), was realized in a structurally flexible metal–organic framework, {Mn7(2,7-AQDC)6(2,6-AQDC)(DMA)6} (AQDC = anthraquinone dicarboxylates, DMA = N,N-dimethylacetamide), with electron-accepting anthraquinone groups, generating two MOF guest charge transfer complexes: {Mn7(2,7-AQDC)6(2,6-AQDC)(DMA)6(TTF)5} and {Mn7(2,7-AQDC)6(2,6-AQDC)(DMA)4(H2O)2(TMPDA)7}. Using a mild impregnation procedure, single crystals of the target complexes were obtained via a crystal-to-crystal conversion, and the crystals were suitable for structural analysis. Single crystal X-ray analysis demonstrated the different arrangements of these intercalated donor molecules: some donor molecules interacted with the anthraquinone groups and formed infinite D–A–A–D stacks, some appeared beside the anthraquinone groups but only formed donor–acceptor pairs, and the remainder of the molecules simply filled the space. The charge transfer between the guests and the framework was spectroscopically confirmed, and the radical densities on the organic species were estimated using magnetic susceptibility measurements. Compared with a solid-state mixture of anthraquinone and donor molecules, the evenly distributed donor molecules in the micropores of the MOF resulted in a “solid solution” state and significantly promoted the degree of charge transfer between donors and acceptors. Such an encapsulation process may be adopted as a new strategy for post-modification of the electronic and magnetic properties of MOFs, as well as for generating new semiconducting charge-transfer complexes.

Graphical abstract: Nanopore-induced host–guest charge transfer phenomena in a metal–organic framework

Back to tab navigation

Supplementary files

Publication details

The article was received on 20 Dec 2017, accepted on 14 Feb 2018 and first published on 15 Feb 2018


Article type: Edge Article
DOI: 10.1039/C7SC05390H
Citation: Chem. Sci., 2018,9, 3282-3289
  • Open access: Creative Commons BY license
  •   Request permissions

    Nanopore-induced host–guest charge transfer phenomena in a metal–organic framework

    S. Yamamoto, J. Pirillo, Y. Hijikata, Z. Zhang and K. Awaga, Chem. Sci., 2018, 9, 3282
    DOI: 10.1039/C7SC05390H

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements