Consequences of the one-electron reduction and photoexcitation of unsymmetric bis-imidazolium salts

Abstract

Coupling of uronium salts with in situ generated N-heterocyclic carbenes provides straightforward access to symmetrical [4](2+) and unsymmetrical bis-imidazolium salts [6](2+) and [9](2+) . As indicated by cyclic and square-wave voltammetry, [6](2+) and [9](2+) can be (irreversibly) reduced by one electron. The initially formed radicals [6](.+) and [9](.+) undergo further reactions, which were probed by EPR spectroscopy and density functional calculations. The final products of the two-electron reduction are the two carbenes. Upon irradiation with UV light both [6](2+) and [9](2+) emit at room temperature in solution but with dramatically different characteristics. The different fluorescence behavior is analyzed by emission spectroscopy and interpreted by using time-dependent density functional calculations as largely due to different excited-state dynamics of [6](2+) and [9](2+) . The geometries of both radicals [6](.+) and [9](.+) and excited states {[6](2+) }* and {[9](2+) }* are substantially different from those of the parent ground-state molecules.