Steric and Electronic Effects of Ligand Substitution on Redox-Active Fe4S4-Based Coordination Polymers

24 May 2021, Version 1


One of the notable advantages of molecular materials is the ability to precisely tune structure, properties, and function via molecular substitutions. While many studies have demonstrated this principle with classic carboxylate‐based coordination polymers, there are comparatively fewer examples where systematic changes to sulfur‐based coordination polymers have been investigated. Here we present such a study on 1D coordination chains of redox‐active
iron-sulfur clusters linked by methylated 1,4‐benzene‐dithiolates. A series of new iron-sulfur based coordination polymers were synthesized with either 2,5‐dimethyl‐1,4‐benzenedithiol (DMBDT) or 2,3,5,6‐tetramethyl‐1,4‐benzenedithiol. The structures of these compounds have been characterized based on synchrotron Xray
powder diffraction while their chemical and physical properties have been characterized by techniques including X‐ray photoelectron spectroscopy, cyclic voltammetry and UV–visible spectroscopy. Methylation results in the general trend of increasing electron‐richness in the series, but the tetramethyl version exhibits unexpected properties arising from steric constraints. All these results highlight how substitutions on organic linkers can modulate electronic factors to fine‐tune the electronic structures of metal‐organic materials.


Supplementary materials



Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.