Journal
FARADAY DISCUSSIONS
Volume 231, Issue -, Pages 152-167Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1fd00021g
Keywords
-
Categories
Funding
- Australian Research Council [FT170100283]
- EPSRC (UK) [NS/A000055/1]
- Australian Government
Ask authors/readers for more resources
Electroactive metal-organic frameworks exhibit multifunctional properties that can be modulated by changing redox states. Studies show that structural modifications influence the degree of electronic coupling and rate of electron transfer.
Electroactive metal-organic frameworks (MOFs) are an attractive class of materials owing to their multifunctional 3-dimensional structures, the properties of which can be modulated by changing the redox states of the components. In order to realise both fundamental and applied goals for these materials, a deeper understanding of the structure-function relationships that govern the charge transfer mechanisms is required. Chemical or electrochemical reduction of the framework [Zn(BPPFTzTz)(tdc)]center dot 2DMF, hereafter denoted ZnFTzTz (where BPPFTzTz = 2,5-bis(3-fluoro-4-(pyridin-4-yl)phenyl)thiazolo[5,4-d]thiazole), generates mixed-valence states with optical signatures indicative of through-space intervalence charge transfer (IVCT) between the cofacially stacked ligands. Fluorination of the TzTz ligands influences the IVCT band parameters relative to the unsubstituted parent system, as revealed through Marcus-Hush theory analysis and single crystal UV-Vis spectroscopy. Using a combined experimental, theoretical and density functional theory (DFT) analysis, important insights into the effects of structural modifications, such as ligand substitution, on the degree of electronic coupling and rate of electron transfer have been obtained.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available