Extended π‐Conjugation and Structural Planarity Effects of Symmetrical D‐π‐A‐π‐D Naphthalene and Perylene Diimide Semiconductors on n‐type Electrical Properties

Abstract

A series of donor‐π‐acceptor‐π‐donor (D‐π‐A‐π‐D) compounds based on naphthalendiimide (NDI) and perylenediimide (PDI) central cores combined with triphenylamine and phenylcarbazole donor groups have been synthesized, characterized and tested in top‐contact/bottom gate organic field‐effect transistors (OFETs). The results showed high electron mobilities, up to 0.3 cm2 V−1 s−1, in the case of NDI derivatives and moderate values of around 10−3 cm2 V−1 s−1 for PDI‐based semiconductors. Quantum chemical calculations were performed in order to support the experimental data. The results suggest that adequate molecular characteristics and larger crystalline domains in NDI vs. PDI semiconducting films may be the reasons behind the enhanced electrical properties of NDI derivatives. Furthermore, when the lateral donor substituents are triphenylamine groups, the mobilities were slightly higher in comparison to phenylcarbazole donor groups due to an improved electron‐donating character. Other characterization techniques, such as AFM, X‐ray diffraction or spectroelectrochemistry, among others, have been performed to analyze supramolecular order, charge carriers’ nature and stability, parameters closely related to charge transport characteristics.

Tuning the charge stabilization and transport in naphthalimide-based semiconductors via a fused-ring and core-engineering strategy

“…26–30 On the other hand, the covalent linkage of naphthalimide units with strong donor scaffolds such as oligothiophenes or triarylamines has shown to be a promising approach to obtain ambipolar materials. 31,32 Thus, in our research groups we have widely demonstrated that the combination of donor and acceptor units through different rigid and conjugated linkers can pave the way to functional materials with tunable and, sometimes unexpected, optical and electrochemical properties and good n-type or ambipolar characteristics in OFETs or OSCs. 33–40…”