| Autor: |
Salinas O; Chemistry, The University of Chicago, Chicago, Illinois, United States. jsanderson@uchicago.edu., Xie J; Chemistry, The University of Chicago, Chicago, Illinois, United States. jsanderson@uchicago.edu., Papoular RJ; Leon Brillouin Laboratory, French Alternative Energies and Atomic Energy Commission Saclay Institute of Matter and Radiation, IRAMIS/CEA-Saclay, Gif-sur-Yvette, Île-de-France, France., Horwitz NE; Chemistry, The University of Chicago, Chicago, Illinois, United States. jsanderson@uchicago.edu., Elkaim E; Synchrotron Soleil, GIF-sur-Yvette, France., Filatov AS; Chemistry, The University of Chicago, Chicago, Illinois, United States. jsanderson@uchicago.edu., Anderson JS; Chemistry, The University of Chicago, Chicago, Illinois, United States. jsanderson@uchicago.edu. |
| Abstrakt: |
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 Fe 4 S 4 clusters linked by methylated 1,4-benzene-dithiolates. A series of new Fe 4 S 4 -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. |
