| Autor: |
Horwitz NE; Department of Chemistry , University of Chicago , Chicago , Illinois 60637 , United States., Xie J; Department of Chemistry , University of Chicago , Chicago , Illinois 60637 , United States., Filatov AS; Department of Chemistry , University of Chicago , Chicago , Illinois 60637 , United States., Papoular RJ; Saclay Institute for Matter and Radiation (IRAMIS) , Leon Brillouin Laboratory, CEA-Saclay , 91191 Gif-sur-Yvette , France., Shepard WE; Synchrotron SOLEIL , L'Orme des Merisiers Saint-Aubin , BP 48, 91192 Gif-sur-Yvette , France., Zee DZ; Department of Chemistry , Northwestern University , Evanston , Illinois 60208 , United States., Grahn MP; Department of Chemistry , University of Chicago , Chicago , Illinois 60637 , United States., Gilder C; Department of Chemistry , University of Chicago , Chicago , Illinois 60637 , United States., Anderson JS; Department of Chemistry , University of Chicago , Chicago , Illinois 60637 , United States. |
| Abstrakt: |
Here we describe the combination of an archetypal redox-active metal sulfide cluster, Fe 4 S 4 , with an organic linker, 1,4-benzenedithiolate, to prepare coordination polymers containing infinite chains of Fe 4 S 4 clusters. The crystal structures of two solid materials have been solved from synchrotron X-ray powder diffraction data using simulated annealing and refined by a least-squares Rietveld refinement procedure. The electronic properties of these chains have also been characterized by UV-visible and Mössbauer spectroscopies. Additional experiments demonstrated that these chains can be solubilized by variation of the countercation and that the chain structure is maintained in solution. The redox-activity of the Fe 4 S 4 clusters can be accessed with chemical reagents. Introduction of charge carriers by reduction of the Fe 4 S 4 clusters is found to increase the electrical conductivity of the materials by up to 4 orders of magnitude. These results highlight the utility of Fe 4 S 4 clusters as redox-active building blocks in preparing new classes of coordination polymers. |
