Programmable Assembly of π-Conjugated Polymers

pi-Conjugated polymers have numerous applications due to their advantageous optoelectronic and mechanical properties. These properties depend intrinsically on polymer ordering, including crystallinity, orientation, morphology, domain size, and pi-pi interactions. Programming, or deliberately controlling the composition and ordering of pi-conjugated polymers by well-defined inputs, is a key facet in the development of organic electronics. Here, pi-conjugated programming is described at each stage of material development, stressing the links between each programming mode. Covalent programming is performed during polymer synthesis such that complex architectures can be constructed, which direct polymer assembly by governing polymer orientation, pi-pi interactions, and morphological length-scales. Solution programming is performed in a solvated state as polymers dissolve, aggregate, crystallize, or react in solution. Solid-state programming occurs in the solid state and is governed by polymer crystallization, domain segregation, or gelation. Recent progress in programming across these stages is examined, highlighting order-dependent features and assembly techniques that are unique to pi-conjugated polymers. This should serve as a guide for delineating the many ways of directing pi-conjugated polymer assembly to control ordering, structure, and function, enabling the further development of organic electronics.

Automated summary

π-Conjugated polymers have unique properties that depend on their ordering, with programming techniques such as covalent and solution programming playing a key role in controlling their assembly. Progress in programming at different stages of material development highlights order-dependent features and unique assembly techniques for pi-conjugated polymers.