Single-crystal polymers (SCPs): from 1D to 3D architectures

Single-crystal polymers (SCPs) with unambiguous chemical structures at atomic-level resolutions have attracted great attention. Obtaining precise structural information of these materials is critical as it enables a deeper understanding of the potential driving forces for specific packing and long-range order, secondary interactions, and kinetic and thermodynamic factors. Such information can ultimately lead to success in controlling the synthesis or engineering of their crystal structures for targeted applications, which could have far-reaching impact. Successful synthesis of SCPs with atomic level control of the structures, especially for those with 2D and 3D architectures, is rare. In this review, we summarize the recent progress in the synthesis of SCPs, including 1D, 2D, and 3D architectures. Solution synthesis, topochemical synthesis, and extreme condition synthesis are summarized and compared. Around 70 examples of SCPs with unambiguous structure information are presented, and their synthesis methods and structural analysis are discussed. This review offers critical insights into the structure-property relationships, providing guidance for the future rational design and bottom-up synthesis of a variety of highly ordered polymers with unprecedented functions and properties. The examples of single-crystal polymers, including 1D, 2D, and 3D architectures with unambiguous chemical structures, are discussed in this review, offering critical insights into their structure-property relationships and design principles.