Deciphering the Multifarious Charge‐Transport Behaviour of Crystalline Propeller‐Shaped Triphenylamine Analogues

A collection of para‐substituted propeller‐shaped triphenylamine (TPA) derivatives have been computationally investigated for charge‐transport characteristics exhibited by the derivatives by using the Marcus–Hush formalism. The various substituents chosen herein, with features that range from electron withdrawing to electron donating in nature, play a key role in defining the reorganisation energy and electronic coupling properties of the TPA derivatives. The TPA moiety is expected to possess weak electronic coupling on the basis of poor orbital overlap upon aggregation, owing to the restriction imposed by the propeller shape of the TPA core. However, the substituent groups attached to the TPA core can significantly dictate the crystal‐packing motif of the TPA derivatives, wherein the variety of noncovalent intermolecular interactions subsequently generated drive the packing arrangement and influence electronic coupling between the neighbouring orbitals. Intermolecular interactions in the crystalline architecture of TPA derivatives were probed by using Hirshfeld and quantum theory of atoms‐in‐molecules techniques. Furthermore, symmetry‐adapted perturbation theory analysis of the TPA analogues has revealed that a periodic arrangement of energetically stable dimers with significant electronic coupling is essential to contribute high charge‐carrier mobility to the overall crystal. Unpacking crystals: Tuning the substituent group attached to the non‐planar triphenylamine (TPA) chromophore plays a vital role in modulating the charge‐transporting capabilities of TPA crystals by significantly affecting the internal reorganisation energy of the molecule, crystal packing and intermolecular electronic coupling efficiency (see figure).