Electron-Deficient Bipyrrole Boomerangs: Bright Fluorophores Obtained via Double C-H Bond Activation

Chemistry. 2018 May 23;24(29):7525-7530. doi: 10.1002/chem.201801199. Epub 2018 Apr 30.

Abstract

PdII -mediated annulative double C-H activation is shown to efficiently convert 1,n-dipyrrolylalkanes into extensively π-conjugated bipyrroles not accessible by conventional oxidative coupling protocols. This approach is applicable to both electron-rich and electron-deficient systems, and has been further developed into tandem processes involving further cyclization of substituents or oxygenation of pyrrolic α-positions. The new bipyrrole intermediates show enhanced fluorescence as well as tunable optical properties controlled by the alignment of chromophore subunits. Photophysical data, including femtosecond transient absorptions, reveal solvent-induced intramolecular charge transfer in their excited states, dependent on the polarity of the medium.

Keywords: C−H activation; charge transfer; fluorescence; helical structures; heterocycles.