Supramolecular Steric Hindrance at Bulky Organic/Polymer Semiconductors and Devices

We initiated both hierarchical chemistry and four-element approach to challenge the complexity of organic devices toward the era of consciousness. Following the concept, a pair of opposites between steric repulsion and non-covalent attraction is uniformed via covalent engineering, making a versatile chemical toolbox to control over the organic/polymer semiconductors. In this chapter, we focus on non-covalent interactions in bulk semiconductors. Supramolecular steric hindrances (SSH) were extracted from spiro- and (di)arylfluorene-based small molecules and polymer semiconductors. Bulk supramolecules, basketweave motifs, a hierarchical chemistry starting from a repulsor–attractor molecular design to nanofilm devices, and supramolecular hindrance polymers have been highlighted in terms of molecular packing, nanostructures, and phase morphology as well as device performance in organic electronics. Finally, we summarized the SSH effect, followed by an outlook on the supramolecular nanomolecules and nanopolymers.