Acenes have received a lot of attention because of their inherent and tunable absorbing, emissive, and charge transport properties for electronic, photovoltaic, and singlet fission applications, among others. Such properties are directly governed by molecular packing, and therefore, controlling their arrangement in the solid state is of utmost importance in order to increase their performance. Herein, we describe a new solid-state ordering strategy that allows obtaining 1D mixed π-stacks of acene and azaacene derivatives. In addition, we illustrate that charge transport can be modulated by the electronic nature of the encapsulated phenazine, opening new perspectives in the design, preparation and development of supramolecular organic semiconductors.
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