Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.



Quantification of the mixed-valence and intervalence charge transfer properties of a cofacial metal–organic framework via single crystal electronic absorption spectroscopy

Author affiliations

Abstract

Gaining a fundamental understanding of charge transfer mechanisms in three-dimensional Metal–Organic Frameworks (MOFs) is crucial to the development of electroactive and conductive porous materials. These materials have potential in applications in porous conductors, electrocatalysts and energy storage devices; however the structure–property relationships pertaining to charge transfer and its quantification are relatively poorly understood. Here, the cofacial Cd(II)-based MOF [Cd(BPPTzTz)(tdc)]·2DMF (where BPPTzTz = 2,5-bis(4-(pyridin-4-yl)phenyl)thiazolo[5,4-d]thiazole, tdc2− = 2,5-thiophene dicarboxylate) exhibits Intervalence Charge Transfer (IVCT) within its three-dimensional structure by virtue of the close, cofacial stacking of its redox-active BPPTzTz ligands. The mixed-valence and IVCT properties are characterised using a combined electrochemical, spectroelectrochemical and computational approach. Single crystal electronic absorption spectroscopy was employed to obtain the solid-state extinction coefficient, enabling the application of Marcus–Hush theory. The electronic coupling constant, Hab, of 145 cm−1 was consistent with the localised mixed-valence properties of both this framework and analogous systems that use alternative methods to obtain the Hab parameter. This work demonstrates the first report of the successful characterisation of IVCT in a MOF material using single crystal electronic absorption spectroscopy and serves as an attractive alternative to more complex methods due to its simplicity and applicability.

Graphical abstract: Quantification of the mixed-valence and intervalence charge transfer properties of a cofacial metal–organic framework via single crystal electronic absorption spectroscopy

Back to tab navigation

Supplementary files

Article information


Submitted
13 Mar 2020
Accepted
20 Apr 2020
First published
24 Apr 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Advance Article
Article type
Edge Article

Quantification of the mixed-valence and intervalence charge transfer properties of a cofacial metal–organic framework via single crystal electronic absorption spectroscopy

P. W. Doheny, J. K. Clegg, F. Tuna, D. Collison, C. J. Kepert and D. M. D'Alessandro, Chem. Sci., 2020, Advance Article , DOI: 10.1039/D0SC01521K

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.


Social activity

Search articles by author

Spotlight

Advertisements