Carrier Charge Polarity in Mixed-Stack Charge-Transfer Crystals Containing Dithienobenzodithiophene

Dithieno­[2,3-d;2′3′-d′]­benzo­[1,2-b;4,5-b′]­dithiophene forms mixed-stack charge-transfer complexes with fluorinated tetracyanoquinodimethanes (F_nTCNQs, n = 0, 2, and 4) and dimethyldicyanoquinonediimine (DMDCNQI). The single-crystal transistors of the F_nTCNQ complexes exhibit electron transport, whereas the DMDCNQI complex shows hole transport as well. The dominance of electron transport is explained by the superexchange mechanism, where transfers corresponding to the acceptor-to-acceptor hopping (t_e^eff) are more than 10 times larger than the donor-to-donor hopping (t_h^eff). This is because the donor orbital next to the highest occupied molecular orbital makes a large contribution to the electron transport owing to the symmetry matching. Like this, inherently asymmetrical electron and hole transport in alternating stacks is understood by analyzing bridge orbitals other than the transport orbitals.