Jump to main content
Jump to site search


Influence of Structure-Activity Relationships on Through-Space Intervalence Charge Transfer in Metal-Organic Frameworks with Cofacial Redox-Active Units

Abstract

Understanding charge transfer in redox-active metal-organic frameworks (MOFs) is of fundamental importance given the potential of these materials to be used in myriad applications including porous conductors, electrocatalysts and battery materials, amongst others. An important challenge is quantifying the spectroscopic features of these materials in order to elucidate their charge transfer properties. Herein, two topologically related Zn(II) and Cd(II) frameworks, [Zn2(DPPTzTz)2(SDC)2] (1-Zn) and [Cd2(DPPTzTz)2(SDC)2] (2-Cd) (where DPPTzTz = 2,5-bis(4-(4-pyridinyl)phenyl)thiazolo[5,4-d]thiazole and SDC = selenophene-2,5-dicarboxylate), incorporating cofacially stacked pairs of redox-active DPPTzTz ligands are presented. The differences in the through-space intervalence charge transfer properties of the mixed-valence forms of the two frameworks generated upon solid state spectroelectrochemical reduction are quantified using Marcus-Hush theory. Further, charge transfer theory is applied to calculate electron mobilities in both extended framework systems. A larger electronic coupling constant, Hab, of 118 cm-1 corresponding to an electron mobility, k, of 6.02 × 108 s-1 was observed for the Zn(II) analogue compared to the Cd(II) analogue (Hab = 61.2 cm-1 and k = 2.22 × 108 s-1) and was correlated primarily with the larger cofacial stacking distance and increasingly offset stacking geometry between DPPTzTz ligands in the latter. Establishing structure-activity relationships in electroactive MOFs, in addition to methods for quantifying their charge transfer properties, represents an important advance in fine tuning solid state materials for device applications.

Back to tab navigation

Supplementary files

Publication details

The article was received on 09 Mar 2018, accepted on 28 Oct 2018 and first published on 29 Oct 2018


Article type: Edge Article
DOI: 10.1039/C8SC01128A
Citation: Chem. Sci., 2019, Accepted Manuscript
  • Open access: Creative Commons BY-NC license
  •   Request permissions

    Influence of Structure-Activity Relationships on Through-Space Intervalence Charge Transfer in Metal-Organic Frameworks with Cofacial Redox-Active Units

    B. Ding, C. Hua, C. J. Kepert and D. M. D'Alessandro, Chem. Sci., 2019, Accepted Manuscript , DOI: 10.1039/C8SC01128A

    This article is licensed under a Creative Commons Attribution-NonCommercial 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 and it is not used for commercial purposes.

    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