The lower charge mobility of organic semiconductors relative to that of inorganic semiconductors is a thorny problem that still has not been resolved.

A series of donor–acceptor “”-shaped gridarenes were synthesized with BT units as the crossbeam and thiophene units as the π-bridge. The donor–acceptor gridization functional effects on optoelectronic properties were then studied experimentally and computationally to provide a platform to adjust the energetics of the highest occupied molecular orbital/lowest unoccupied molecular orbital levels. Finally, G-DTh-based two-terminal memristor indium tin oxide/G-DTh:TBAPF6/Al successfully realizes conventional learning processes, synaptic potentiation, and depression plasticity which are essential for neuromorphic computation.

Summary of main observation and conclusion Organic semiconductor materials with low reorganization energy have various applications such as in organic light‐emitting diodes (OLEDs), organic field‐effect transistor (OFETs) and organic solar cells (OSCs). In this work, we have designed a new class of gridspiroarenes (GS‐SFX and GS‐SITF) with #‐shaped structures, which have novel crisscross geometrical structures compared to widely used spirocyclic arenes—SFX and SITF. The structure electronic properties, adiabatic ionization potentials (IPa), adiabatic electron affinities (EAa) and reorganization energies (λ) of GS‐SFX and GS‐SITF have been calculated using density functional theory (DFT) method. The calculated HOMO and LUMO spatial distributions suggest that GS‐SFX and GS‐SITF have better transport properties. The noncovalent interaction analysis shows the weak intramolecular interactions between their arms. The results indicate that the reorganization energies of GS‐SFX and GS‐SITF are significantly reduced compared to the dimer structures—DSFX and DSITF. Furthermore, the GS‐SITF1 which is one of the isomers of GS‐SITF exhibits the lowest values for λ(h) (0.067 eV) and λ(e) (0.153 eV). Therefore, we believe the predicted structure, electronic property, and reorganization energy are good indicator for transport materials. This work has systematically studied the effect of gridization, which provides insights to design organic semiconductor materials with excellent charge transport properties.