104014-86-0Relevant articles and documents
Steric and electronic effects of ligand substitution on redox-active Fe4S4-based coordination polymers
Anderson, John S.,Elkaim, Erik,Filatov, Alexander S.,Horwitz, Noah E.,Papoular, Robert J.,Salinas, Omar,Xie, Jiaze
, p. 10798 - 10805 (2021/08/17)
One of the notable advantages of molecular materials is the ability to precisely tune structure, properties, and functionviamolecular 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 Fe4S4clusters linked by methylated 1,4-benzene-dithiolates. A series of new Fe4S4-based coordination polymers were synthesized with either 2,5-dimethyl-1,4-benzenedithiol (DMBDT) or 2,3,5,6-tetramethyl-1,4-benzenedithiol (TMBDT). The structures of these compounds have been characterized based on synchrotron X-ray 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.
