Wurster's blue-type cation radicals framed in a 5,10-Dihydrobenzo[a] indolo[2,3-c]carbazole (BIC) Skeleton: Dual electrochromism with drastic changes in UV/Vis/NIR and fluorescence

Abstract

Electron-donating dihydrobenzindolocarbazoles (BICs) 1 a-c, which adopt planar disk-shaped geometries, were prepared by gold(I)-catalyzed cyclization as a key step. Due to the presence of a 1,4-phenylenediamine (PD) moiety in the framework, they undergo reversible one-electron oxidation to the corresponding Wurster's Blue (WB)-type species that exhibits NIR absorptions up to λ=1200 nm. In the case of the N,N -dimethyl derivative, cation radical 1 c+. is stable enough to be isolated as a salt and X-ray analysis indicated paraquinoid-type bond alternation in the WB core unit, whereas the bond lengths in the peripheral benzene rings are identical to those in the neutral donor. Upon electrochemical interconversion, the redox pairs of 1 a-c and 1 a-c+. exhibited an electrochromic response in the UV/Vis/NIR region, which was accompanied by a drastic change in the fluorescence spectrum because only neutral donors 1 a-c are highly emissive (ΦF: 0.7-0.8). Potential for change: Both UV/Vis/NIR and fluorescence can be reversibly modified by application of electric potential to the highly fluorescent π-extended p-phenylenediamines with disk-shaped geometries to form stable cation radical species (see figure). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.