NIR absorbing ferrocenyl perylenediimide-based donor–acceptor chromophores

Abstract

A set of ferrocenyl-functionalized perylenediimide (PDI) compounds and their 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) derivatives 1–5 were designed and synthesized using palladium-catalyzed Sonogashira cross-coupling, followed by a thermally activated [2 + 2] cycloaddition–retroelectrocyclization [CA–RE] reaction with a 1,1,2,2-tetracyanoethylene (TCNE) acceptor in good yields. The TCBD group works as an acceptor, whereas the ferrocenyl group acts as a donor at the central PDI core. The effects of varying the number of ferrocenyl and TCNE groups on the photophysical, thermal, electrochemical, and spectroelectrochemical properties were studied. The di-substituted PDI derivatives 3, 4, and 5 exhibit bathochromic shifts in the absorption spectra compared to 1 and 2, attributed to the extended π-conjugation. The electrochemical analysis of derivatives 2, 4, and 5 shows multiple reduction waves in the low potential region due to the presence of TCBD and perylenediimide acceptor units. Spectroelectrochemical studies were performed, showing that upon applying redox potentials, the absorption spectra shifted from the visible to the near-infrared (NIR) region. Computational calculations indicate that in the HOMO, the electron density is localized on the ferrocene unit, while in the LUMO, it is distributed over the PDI–TCBD unit, indicating a strong D–A interaction.