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Herein, we report structural, computational, and conductivity studies on urea-directed self-assembled iodinated triphenylamine (TPA) derivatives. Despite numerous reports of conductive TPAs, the challenges of correlating their solid-state assembly with charge transport properties hinder the efficient design of new materials. In this work, we compare the assembled structures of a methylene urea bridged dimer of di-iodo TPA (1) and the corresponding methylene urea di-iodo TPA monomer (2) with a di-iodo mono aldehyde (3) control. These modifications lead to needle shaped crystals for 1 and 2 that are organized by urea hydrogen bonding, π⋯π stacking, I⋯I, and I⋯π interactions as determined by SC-XRD, Hirshfeld surface analysis, and X-ray photoelectron spectroscopy (XPS). The long needle shaped crystals were robust enough to measure the conductivity by two contact probe methods with 2 exhibiting higher conductivity values (∼6 × 10 −7 S cm −1 ) compared to 1 (1.6 × 10 −8 S cm −1 ). Upon UV-irradiation, 1 formed low quantities of persistent radicals with the simple methylurea 2 displaying less radical formation. The electronic properties of 1 were further investigated using valence band XPS, which revealed a significant shift in the valence band upon UV irradiation (0.5–1.9 eV), indicating the potential of these materials as dopant free p-type hole transporters. The electronic structure calculations suggest that the close packing of TPA promotes their electronic coupling and allows effective charge carrier transport. Our results show that ionic additives significantly improve the conductivity up to ∼2.0 × 10 −6 S cm −1 in thin films, enabling their implementation in functional devices such as perovskite or solid-state dye sensitized solar cells. 

Absorption of electronic acceptors in the accessible channels of an assembled triphenylamine (TPA) bis -urea macrocycle 1 enabled the study of electron transfer from the walls of the TPA framework to the encapsulated guests. The TPA host is isoskeletal in all host–guest structures analyzed with guests 2,1,3-benzothiadiazole, 2,5-dichlorobenzoquinone and I 2 loading in single-crystal-to-single-crystal transformations. Analysis of the crystal structures highlights how the spatial proximity and orientation of the TPA host and the entrapped guests influence their resulting photophysical properties and allow direct comparison of the different donor–acceptor complexes. Diffuse reflectance spectroscopy shows that upon complex formation 1·2,5-dichlorobenzoquinone exhibits a charge transfer (CT) transition. Whereas, the 1·2,1,3-benzothiadiazole complex undergoes a photoinduced electron transfer (PET) upon irradiation with 365 nm LEDs. The CT absorptions were also identified with the aid of time dependent density functional theory (TD-DFT) calculations. Cyclic voltammetry experiments show that 2,1,3-benzothiadiazole undergoes reversible reduction within the host–guest complex. Moreover, the optical band gaps of the host 1·2,5-dichlorobenzoquinone (1.66 eV), and host 1·2,1,3-benzothiadiazole (2.15 eV) complexes are significantly smaller as compared to the free host 1 material (3.19 eV). Overall, understanding this supramolecular electron transfer strategy should pave the way towards designing lower band gap inclusion complexes.