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Abstract The crystal structures of the charge‐transfer (CT) cocrystals formed by the π‐electron acceptor 1,3,4,5,7,8‐hexafluoro‐11,11,12,12‐tetracyanonaphtho‐2,6‐quinodimethane (F₆TNAP) with the planar π‐electron‐donor molecules triphenylene (TP), benzo[b]benzo[4,5]thieno[2,3‐d]thiophene (BTBT), benzo[1,2‐b:4,5‐b′]dithiophene (BDT), pyrene (PY), anthracene (ANT), and carbazole (CBZ) have been determined using single‐crystal X‐ray diffraction (SCXRD), along with those of two polymorphs of F₆TNAP. All six cocrystals exhibit 1:1 donor/acceptor stoichiometry and adopt mixed‐stacking motifs. Cocrystals based on BTBT and CBZ π‐electron donor molecules exhibit brickwork packing, while the other four CT cocrystals show herringbone‐type crystal packing. Infrared spectroscopy, molecular geometries determined by SCXRD, and electronic structure calculations indicate that the extent of ground‐state CT in each cocrystal is small. Density functional theory calculations predict large conduction bandwidths and, consequently, low effective masses for electrons for all six CT cocrystals, while the TP‐, BDT‐, and PY‐based cocrystals are also predicted to have large valence bandwidths and low effective masses for holes. Charge‐carrier mobility values are obtained from space‐charge limited current (SCLC) measurements and field‐effect transistor measurements, with values exceeding 1 cm²V⁻¹s¹being estimated from SCLC measurements for BTBT:F₆TNAP and CBZ:F₆TNAP cocrystals. 

The electronic, vibrational, and charge-transport properties of a series of benzothieno-benzothiophene (BTBT)–F m TCNQ ( m = 0, 2, 4) and diC n BTBT–F m TCNQ ( n = 8, 12; m = 0, 4) donor–acceptor (DA) co-crystals have been investigated by means of density functional theory calculations. The electronic-structure calculations predict wide conduction bands and small effective masses for electrons along the DA stacking directions. The results indicate that the increase in the number of F atoms on the acceptor molecules results in an increase of superexchange couplings along the DA stacks, while the addition of the alkyl side chains results in a decrease of through-space transfer integrals between neighboring stacks. Time-dependent density functional theory calculations of the optical properties describe the lowest two optical transitions as having a charge-transfer character and being related to the two electronic coupling pathways that contribute to the superexchange couplings. The results also indicate that the ionicity parameter in the diC n BTBT–F m TCNQ cocrystals is somewhat larger than in the BTBT analogues. Overall, we find that DFT calculations based on periodic boundary conditions are a reliable tool to estimate the ionicity parameter in DA cocrystals.