Pentacene derivative/DTTCNQ cocrystals: alkyl-confined mixed heterojunctions with molecular alignment and transport property tuning†
Organic cocrystals are formed via the self-assembly of donor and acceptor constituents, which are mixed together through weak noncovalent interactions. Although they reveal unique physical features, their synthesis still faces major drawbacks for the introduction of more potential semiconductors. Herein, we first report soluble pentacene derivative (TMTES-P) based complexes, with suitable alkyl terminal groups, enabling the location of 4,8-bis(dicyanomethylene)-4,8-dihydrobenzo[1,2-b:4,5-b′]-dithiophene (DTTCNQ) in the crystal lattice, thereby allowing the cocrystallization of a binary system on demand. To our surprise, via varying growth conditions, molecular disorders could be removed due to existing short-contacts as the locking force, and even the carrier charge could be changed. This organic donor–acceptor system presents unconventional insights: charge polarity control over (opto)electronic devices with a supramolecular driving force as the directional alignment guide.