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- Title
Unraveling two distinct polymorph transition mechanisms in one n-type single crystal for dynamic electronics.
- Authors
Davies, Daniel William; Seo, Bumjoon; Park, Sang Kyu; Shiring, Stephen B.; Chung, Hyunjoong; Kafle, Prapti; Yuan, Dafei; Strzalka, Joseph W.; Weber, Ralph; Zhu, Xiaozhang; Savoie, Brett M.; Diao, Ying
- Abstract
Cooperativity is used by living systems to circumvent energetic and entropic barriers to yield highly efficient molecular processes. Cooperative structural transitions involve the concerted displacement of molecules in a crystalline material, as opposed to typical molecule-by-molecule nucleation and growth mechanisms which often break single crystallinity. Cooperative transitions have acquired much attention for low transition barriers, ultrafast kinetics, and structural reversibility. However, cooperative transitions are rare in molecular crystals and their origin is poorly understood. Crystals of 2-dimensional quinoidal terthiophene (2DQTT-o-B), a high-performance n-type organic semiconductor, demonstrate two distinct thermally activated phase transitions following these mechanisms. Here we show reorientation of the alkyl side chains triggers cooperative behavior, tilting the molecules like dominos. Whereas, nucleation and growth transition is coincident with increasing alkyl chain disorder and driven by forming a biradical state. We establish alkyl chain engineering as integral to rationally controlling these polymorphic behaviors for novel electronic applications. Cooperative transitions have acquired much attention for low transition barriers, ultrafast kinetics, and structural reversibility but cooperative transitions are rare in molecular crystals and their origin is poorly understood. Here the authors show that reorientation of the alkyl side chains in a 2-dimensional quinoidal terthiophene triggers cooperative behavior, and establish alkyl chain engineering to control the polymorphic behavior.
- Subjects
SINGLE crystals; MOLECULAR crystals; AUTOMATIC control systems; DISCONTINUOUS precipitation; N-type semiconductors; ORGANIC semiconductors; THIOPHENES
- Publication
Nature Communications, 2023, p1
- ISSN
2041-1723
- Publication type
Article
- DOI
10.1038/s41467-023-36871-9