Design of Open‐Shell π‐Conjugated Microporous Polymer Film with Super‐High Conductivity

• Published in: Macromolecular chemistry and physics Vol. 219; no. 9
• Main Author: Xu, Lai
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 01.05.2018
• Subjects: Conductivity; conjugated microporous polymers; Design; Electron transfer; electronic hopping rates; electropolymerization; Molecular chains; Molecular orbitals; Molecular structure; open‐shell organic radicals; Organic materials; Polymer films; Polymerization; Polymers
• ISSN: 1022-1352; 1521-3935
• DOI: 10.1002/macp.201700600

Polymers with open‐shell π‐conjugated structure and thiophene‐based building blocks are designed for electropolymerization. These systems are expected to electropolymerize and form solution‐processable conjugated microporous polymer films, which can be used for device fabrications. The designed radical structure has a low highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap, high electronic hopping rate for the hole transfer and electron transfer, and ultimately high conductivity. The eclipsed dimer has higher conductivities than that of staggered dimer. The designed monomer with substituted groups has lower conductivities due to steric effect. The open‐shell systems designed will be promising materials with various applications. Design principles for open‐shell organic materials can be established based on the trends of this paper. Open‐shell systems connected by thiophene groups are designed for the first time, for polymer film production. It shows that the open‐shell systems have high conductivity and high electronic hopping rate. The predicted open‐shell systems are significant for designing highly conductive polymer films for device fabrication. The design principle for open‐shell organic materials can also be established.