Synthesis, photophysical and electronic properties of tetra-donor- or acceptor-substitutedortho-perylenes displaying four reversible oxidations or reductions

• DOI: 10.1039/c9sc02420d
• Publication Date: 2019-06-25T14:01:36Z
• Authors: Julia Merz; Andreas Steffen; Jörn Nitsch; Julian Fink; Claudia B. Schürger; Alexandra Friedrich; Ivo Krummenacher; Holger Braunschweig; Michael Moos; David Mims; Christoph Lambert; Todd B. Marder
• Keywords: Tetra; Acceptor

Via regioselective Ir-catalyzed C-H borylation and subsequent reactions (i.e., via Br4-Per or (BF3K)4-Per intermediates), we have introduced strong π-donors acceptors at the 2,5,8,11-positions of perylene leading to unusual properties. Thus, incorporation four donor diphenylamine (DPA) acceptor Bmes2 (mes = 2,4,6-Me3C6H2) moieties yields novel compounds which can be reversibly oxidized reduced times, respectively, an unprecedented behavior for monomeric derivatives. Spectroelectrochemical measurements show NIR absorptions up 3000 nm mono-cation radical (DPA)4-Per a electronic coupling over bridge was observed indicative fully delocalized Robin-Day Class III behavior. Both (Bmes2)4-Per derivatives possess unusually long intrinsic singlet lifetimes (τ 0), e.g., 94 ns former one. The are emissive in solution, thin films, solid state, with apparent Stokes shifts that exceptionally large Transient absorption on reveal additional excited lifetime 500 μs, sensitizes oxygen effectively.