Rh(I) diisocyanide coordination polymers have been previously reported as polycrystalline powders,1 but their potential for practical applications such as electrochemical catalyst heterogenization and semiconductor materials have not been previously explored. We have developed synthetic strategies to improve their crystallinity and to expand the scope of aryl diioscyanide linkers to include 5,5′-diisocyanide-2,2′-bipyridine and other linkers as indicated in the attached image. Through strategic synthesis conditions and sequence, we have been able to selectively metallate the 5,5′-diisocyanide-2,2′-bipyridine ligand with Rh(I) at the isocyanide sites and Re(CO)3Cl or Mn(CO)3Br at the bipyridine site, to create analogs of known CO2 reduction catalysts, Re(2,2′-bipyridine)(CO)3Cl and Mn(2,2′-bipyridine)(CO)3Br.2 Structural characterization by PXRD, FT-IR, and XPS demonstrates achievement of the target extended supramolecular structures for a series of diisocyanides. Furthermore, we have prepared these coordination polymer materials from a seed layer of self-assembled diisocyanide on gold electrode surfaces, in order to heterogenize the catalyst on an electrode surface. We are exploring the electrochemical behavior of these films, as well as their conductivity and photoconductivity.

Rh(I) diisocyanide coordination polymers for electrochemical catalyst heterogenization and semiconductor material applications

255th National Meeting (2018)

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