A Convenient N-Arylation Route for Electron-Deficient Pyridines: The Case of π-Extended Electrochromic Phosphaviologens.
A simple and representative procedure for the synthesis of N,N'-diarylated phosphaviologens directly from both electron-rich and electron-poor diaryliodonium salts and 2,7-diazadibenzophosphole oxide is reported. The latter are electron-deficient congeners of the widely utilized N,N'-disubstituted 4,4'-bipyridinium cations, also known as viologens, that proved to be inaccessible by the classical two-step route. The single-step preparation method for phosphaviologens described herein could be extended to genuine viologens but reached its limit when sterically demanding diaryliodonium salts were used. The studied phosphaviologens feature a significantly lowered reduction threshold as compared to all other (phospha)viologens known to date due to the combination of an extended π-system with an electron deficient phosphole core. In addition, a considerably smaller HOMO-LUMO gap was observed due to efficient π-delocalization across the phosphaviologen core, as well as the N-aryl substituents, which was corroborated by quantum chemical calculations. Detailed characterizations of the singly reduced radical species by EPR spectroscopy and DFT calculations verified delocalization of the radical over the extended π-system. Finally, to gain deeper insight into the suitability of the new compounds as electroactive and electrochromic materials, multicolored proof-of-concept electrochomic devices were manufactured.
Department of Chemistry and Centre for Advanced Solar Materials, University of Calgary , 2500 University Drive Northwest, Calgary, Alberta T2N 1N4, Canada.
Christian
C
Reus
Department of Chemistry and Centre for Advanced Solar Materials, University of Calgary , 2500 University Drive Northwest, Calgary, Alberta T2N 1N4, Canada.
Monika
M
Stolar
Department of Chemistry and Centre for Advanced Solar Materials, University of Calgary , 2500 University Drive Northwest, Calgary, Alberta T2N 1N4, Canada.
Jeffrey
J
Vanderkley
Department of Chemistry and Centre for Advanced Solar Materials, University of Calgary , 2500 University Drive Northwest, Calgary, Alberta T2N 1N4, Canada.|Department für Chemie und Pharmazie & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU) , Henkestrasse 42, 91054 Erlangen, Germany.
Johannes
J
Nebauer
Department of Chemistry and Centre for Advanced Solar Materials, University of Calgary , 2500 University Drive Northwest, Calgary, Alberta T2N 1N4, Canada.
Thomas
T
Baumgartner