Despite the great advances in the synthesis of diverse nonplanar graphenoids, investigations into the relationship between structural features and intermolecular interactions still present significant challenges. Herein, the novel nonplanar graphenoid structure, corannurylene pentapetalae (CRP), obtained via bottom-up syntheses of hybridization between perylene diimide (PDI) planar fragments and a corannulene curved core, is presented. Single crystal studies reveal a D 5-symmetric as well as a C 2-symmetric graphenoid corannurylene pentapetalae. The D 5-symmetric structure has a unique honeycomb lattice with two chiral honeycomb layers alternately stacked, whereas the C 2-symmetric CRP forms dimer units via π–π stacking. Transistor devices demonstrate that, without any π–π stacking, the honeycomb lattice of the D 5-symmetric CRP has the potential to also facilitate electron transport.

Acene imides are expected to possess smaller band gaps than homologous acenes while maintaining good solubility and stability. However, the design and synthesis of large acene imides are still a big challenge. Herein, we report a one-pot synthesis of hexacene diimides (HDI) by double aromatic annulation between zirconabenzocyclopentene and tetrabrominated naphthalene diimides. HDIs with branched alkyl chains exhibit very good solubility, stability, and much smaller band gaps than hexacene. Organic field-effect transistors (OFETs) based on HDI microribbons exhibit excellent ambipolar transport behavior with the highest electron mobility of 2.17 cm V s and hole mobility of 0.30 cm V s under ambient conditions.

Three acene-extended triptycenes, TIPS-Antrip, TIPS-Tetrip, and TIPS-Pentrip, which contain TIPS-ethynyl functionalized anthracene, tetracene, and pentacene as subunits, respectively, are synthesized and characterized. It is found that the optoelectronic properties and crystal packing motifs could be modulated by changing the subunits. A preliminary exploration of the excited-state behavior of these molecules indicates that TIPS-Tetrip and TIPS-Pentrip exhibit intramolecular singlet fission (iSF).

Fully non-fused electron acceptors (FNEAs) have shown a promising prospect for commercial applications of organic solar cells (OSCs) due to their simple structures and low costs. Herein, two terthiophene-based NFEAs...

Chlorination of π‐conjugated backbones is garnering great interest because of fine‐tuning electronic properties of conjugated materials for organic devices. Herein we report a synthesis of thiophene‐based diketopyrrolopyrrole (DPP) dimers and their chlorinated counterparts by introducing a chlorine atom in the outer thiophene ring to investigate the influence of the chlorination on charge transport. The backbone chlorination lowers both the HOMO and the LUMO of the dimers and leads to a blue‐shift of maximum absorption in compared to unsubstituted counterparts. X‐ray analysis reveals that the chlorine atom prompts the outer thiophene ring out of the planarity of the backbone with a relatively large torsional angle. The chlorinated dimers exhibit slipped one‐dimensional packing decorated with multiple intermolecular interactions, because of a combination of a negative inductive effect and a positive mesomeric effect of the halogen atom, which might facilitate charge transport within the oligomeric backbones. The mobility in the single‐crystal OFET devices of the chlorinated dimers is up to 1.5 cm2 V−1 s−1, which is two times higher than that of the non‐chlorinated DPP dimers. Our results indicate that the chlorine atom plays a key role in directing non‐covalent interactions to lock the slipped stacks, enabling electronic coupling between adjacent molecules for efficient charge transport. In addition, our results also demonstrate that these DPP dimers with straight n‐octyl chains exhibit higher mobilities than the dimers with branched 2‐ethylhexyl chains.