Mechanistic View on the Order-Disorder Phase Transition in Amphidynamic Crystals

Maor Asher; Marco Bardini; Luca Catalano; Rémy Jouclas; Guillaume Schweicher; Jie Liu; Roman Korobko; Adi Cohen; Yves Geerts; David Beljonne; Omer Yaffe

doi:10.1021/acs.jpclett.2c03316

Mechanistic View on the Order-Disorder Phase Transition in Amphidynamic Crystals

Maor Asher, Marco Bardini, Luca Catalano, Rémy Jouclas, Guillaume Schweicher, Jie Liu, Roman Korobko, Adi Cohen, Yves Geerts, David Beljonne, Omer Yaffe^*

^*Corresponding author for this work

Department of Chemical and Biological Physics

Research output: Contribution to journal › Article › peer-review

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Abstract

We combine temperature-dependent low-frequency Raman measurements and first-principles calculations to obtain a mechanistic understanding of the order–disorder phase transition of 2,7-di-tert-butylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene (ditBu-BTBT) and 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-pentacene) semiconducting amphidynamic crystals. We identify the lattice normal modes associated with the phase transition by following the position and width of the Raman peaks with temperature and identifying peaks that exhibit nonlinear dependence toward the phase transition temperature. Our findings are interpreted according to the “hardcore mode” model previously used to describe order–disorder phase transitions in inorganic and hybrid crystals with a Brownian sublattice. Within the framework of this model, ditBu-BTBT exhibits an ideal behavior where only one lattice mode is associated with the phase transition. TIPS-pentacene deviates strongly from the model due to strong interactions between lattice modes. We discuss the origin of the different behaviors and suggest side-chain engineering as a tool to control polymorphism in amphidynamic crystals.

Original language	English
Pages (from-to)	1570-1577
Number of pages	8
Journal	Journal of Physical Chemistry Letters
Volume	14
Issue number	6
Early online date	7 Feb 2023
DOIs	https://doi.org/10.1021/acs.jpclett.2c03316
Publication status	Published - 16 Feb 2023

Funding

Funding Information: We thank Lior Segev for software development. O.Y. acknowledges funding from the European Research Counsel (850041-ANHARMONIC). Y.G. is thankful to the Belgian National Fund for Scientific Research (FNRS) for financial support through research projects Pi-Fast (No T.0072.18), Pi-Chir (No T.0094.22), DIFFRA (No U.G001.19), 2D to 3D (No O.005018F), and CHISUB (No O.00322). Financial support from the French Community of Belgian (ARC No. 20061) is also acknowledged. L.C. thanks the H2020 MSCA COFUND IF@ULB program for financial support (Grant Agreement 801505). G.S. is a FNRS Research Associate and acknowledges financial support from the Francqui Foundation (Francqui Start-Up Grant). D.B. is a FNRS research director. The work in Mons has been supported by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS) under Grant No. 2.5020.11. This project has received funding from the European Union’s Horizon 2020 research and innovation program under Marie Skodowska-Curie Grant Agreements No. 811284 (UHMob) and No. 801505. Publisher Copyright: © 2023 The Authors. Published by American Chemical Society.

All Science Journal Classification (ASJC) codes

General Materials Science
Physical and Theoretical Chemistry

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oy_JourPhysChemLetters_MechanisticViewOrder-Disorder_PV_2023Final published version, 4.21 MBLicence: CC BY

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title = "Mechanistic View on the Order-Disorder Phase Transition in Amphidynamic Crystals",

abstract = "We combine temperature-dependent low-frequency Raman measurements and first-principles calculations to obtain a mechanistic understanding of the order–disorder phase transition of 2,7-di-tert-butylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene (ditBu-BTBT) and 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-pentacene) semiconducting amphidynamic crystals. We identify the lattice normal modes associated with the phase transition by following the position and width of the Raman peaks with temperature and identifying peaks that exhibit nonlinear dependence toward the phase transition temperature. Our findings are interpreted according to the “hardcore mode” model previously used to describe order–disorder phase transitions in inorganic and hybrid crystals with a Brownian sublattice. Within the framework of this model, ditBu-BTBT exhibits an ideal behavior where only one lattice mode is associated with the phase transition. TIPS-pentacene deviates strongly from the model due to strong interactions between lattice modes. We discuss the origin of the different behaviors and suggest side-chain engineering as a tool to control polymorphism in amphidynamic crystals.",

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AU - Liu, Jie

AU - Korobko, Roman

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AU - Beljonne, David

AU - Yaffe, Omer

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Mechanistic View on the Order-Disorder Phase Transition in Amphidynamic Crystals

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