Reductive Aromatization of 5,7,12,14-Pentacenetetrone: Approach Towards Substituted Pentacenes?

Herein we report a convenient access to asymmetrically substituted, well soluble pentacene derivatives synthesized from commercially available 5,7,12,14-pentacenetetrone via reductive one step functionalization. Zinc or potassium are used as reducing agents and the reduced intermediates are trapped with electrophiles such as acetyl, triisopropylsilyl or cationic methyl synthons. The reduction allows for an unsymmetric functionalization whilst one dione moiety is maintained due to partial reduction. The resulting dyes are characterized by UV/Vis and photoluminescence spectroscopy. Their redox potentials are studied by cyclic voltammetry. The experimentally determined molecular frontier orbital energies are rationalized by density functional theory. The spatial molecular packing motive in the solid state is studied as a function of the substituent size by X-ray crystallography. Attempts of reducing the second quinone moiety towards a functionalized pentacene led to an over-reduced 6,13-dihydropentacene derivative, which by means of an XRD structural analysis surprisingly displays a planar molecular conformation and unique optoelectronic properties.