Unraveling two distinct polymorph transition mechanisms in one n-type single crystal for dynamic electronics.

Autor: Davies DW; Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL, 61801, USA., Seo B; Davidson School of Chemical Engineering, Purdue University, 480 W Stadium Ave, West Lafayette, IN, 47907, USA.; Department of Chemical and Biomolecular Engineering, Seoul National University of Science and Technology, 232 Gongneung-ro, Nowon-gu, Seoul, 01811, Republic of Korea., Park SK; Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL, 61801, USA.; Institute of Advanced Composite Materials, Korea Institute of Science and Technology, Joellabuk-do, 55324, South Korea., Shiring SB; Davidson School of Chemical Engineering, Purdue University, 480 W Stadium Ave, West Lafayette, IN, 47907, USA., Chung H; Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL, 61801, USA., Kafle P; Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL, 61801, USA., Yuan D; Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.; College of Materials Science and Engineering, Hunan University, Changsha, 410082, China., Strzalka JW; X-Ray Science Division, Argonne National Laboratory, Argonne, IL, 60439, USA., Weber R; Bruker BioSpin Corp., 15 Fortune Drive, Billerica, MA, 01821, USA., Zhu X; Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China., Savoie BM; Davidson School of Chemical Engineering, Purdue University, 480 W Stadium Ave, West Lafayette, IN, 47907, USA. bsavoie@purdue.edu., Diao Y; Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL, 61801, USA. yingdiao@illinois.edu.; Beckman Institute for Advanced Science and Technology, 405 N. Mathews Ave. M/C 251, Urbana, IL, 61801, USA. yingdiao@illinois.edu.
Jazyk: angličtina
Zdroj: Nature communications [Nat Commun] 2023 Mar 21; Vol. 14 (1), pp. 1304. Date of Electronic Publication: 2023 Mar 21.
DOI: 10.1038/s41467-023-36871-9
Abstrakt: 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.
(© 2023. The Author(s).)
Databáze: MEDLINE
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