Triisopropylsilylethynyl-substituted indenofluorenes: carbonyl versus dicyanovinylene functionalization in one-dimensional molecular crystals and solution-processed n-channel OFETs

Abstract

The design and synthesis of novel electron-deficient and solution-processable polycyclic aromatic hydrocarbons offers great opportunities for the development of low-cost and large-area (opto)electronics. Although (trialkylsilyl)ethynyl (R₃Si–CC–) has emerged as a very popular unit to solubilize organic semiconductors, it has been applied only to a limited class of materials that are mostly substituted on short molecular axes. Herein, two novel solution-processable indenofluorene-based semiconductors, TIPS-IFDK and TIPS-IFDM, bearing (triisopropylsilyl)ethynyl end units at 2,8-positions (long molecular axis substitution) were synthesized, and their single-crystal structures, optoelectronic properties, solution-sheared thin-film morphologies/microstructures, and n-channel field-effect responses were studied. In accordance with the DFT calculations, the HOMO/LUMO energies of the new compounds are found to be −5.77/−3.65 eV and −5.84/−4.18 eV for TIPS-IFDK and TIPS-IFDM, respectively, reflecting the high electron deficiency of the new π-backbones. Both semiconductors exhibit slightly S-shaped molecular frameworks with highly coplanar IFDK/IFDM π-cores, and they form slipped π-stacked one-dimensional (1-D) columnar motifs in the solid state. However, substantial differences in the degree of π–π interactions and stacking distances (4.04 Å vs. 3.47 Å) were observed between TIPS-IFDK and TIPS-IFDM as a result of carbonyl vs. dicyanovinylene functionalization, which results in a three orders of magnitude variation in the charge carrier mobility of the corresponding thin films. Top-contact/bottom-gate OFETs fabricated via solution-shearing TIPS-IFDM yielded one of the best performances in the (trialkylsilyl)ethynyl literature (μ_e = 0.02 cm² V⁻¹ s⁻¹, I_on/I_off = 10⁷–10⁸, and V_T ∼ 2 V under ambient atmosphere) for a 1-D polycrystalline semiconductor microstructure. To the best of our knowledge, the molecules presented here are the first examples of n-type semiconductors substituted with (trialkylsilyl)ethynyl groups on their long molecular axes.