Ion Transport in 2D Nanostructured $\pi$-Conjugated Thieno[3,2-b]thiophene-Based Liquid Crystal

Wang, Zhongyang; Wang, Chaoqiuyu; Sun, Yangyang; Wang, Kai; Strzalka, Joseph W.; Patel, Shrayesh N.; Nealey, Paul F.; Ober, Christopher K.; Escobedo, Fernando A.

doi:10.1021/acsnano.2c07789

Title: Ion Transport in 2D Nanostructured $$\pi$$-Conjugated Thieno[3,2-b]thiophene-Based Liquid Crystal

Journal Article · Wed Dec 07 00:00:00 EST 2022 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.2c07789· OSTI ID:1909462

^[1]; Wang, Chaoqiuyu ^[2];

^[2]; Wang, Kai ^[1];

^[3];

^[1];

^[2];

^[2]

Univ. of Chicago, IL (United States)
Cornell Univ., Ithaca, NY (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

Leveraging the self-assembling behavior of liquid crystals designed for controlling ion transport is of both fundamental and technological significance. Here, we have designed and prepared a liquid crystal that contains (2,5-bis(5-(2,5,8,11-tetraoxatridecan-13-yl)thiophen-2yl)thieno[3,2-b]thiophene (BTTT) as mesogenic core and conjugated segment and symmetric tetra(ethylene oxide) (EO4) as polar side chains for ionic conducting regions. Driven by the crystallization of the BTTT cores, BTTT/dEO4 exhibits well-ordered smectic phases below 71.5 °C as confirmed by differential scanning calorimetry, polarized optical microscope, temperature dependent wide-angle X-ray scattering and grazing incidence wide-angle X-ray scattering (GIWAXS). We adopted a combination of experimental GIWAXS and molecular dynamics (MD) simulations to better understand the molecular packing of BTTT/dEO4 films, particularly when loaded with the ion conducting salt, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Ionic conduction of BTTT/dEO4 is realized by the addition of LiTFSI, with the material able to maintain smectic phases up to r = [Li⁺]/[EO] = 0.1. In this work, The highest ionic conductivity of 8 × 10^-3 S/cm was attained at an intermedium salt concentration of r = 0.05. It was also found that ion conduction in BTTT/dEO4 is enhanced by forming a smectic layered structure with irregular interfaces between the BTTT and EO4 layers and by the lateral film expansion upon salt addition. This can be explained by the enhancement of the misalignment and configurational entropy of the side chains, which increase their local mobility and that of the solvated ions. Our molecular design thus illustrates how, beyond the favorable energetic interactions that drive the assembly and ion solvating domains, modulation of entropic effects can also be favorably harnessed to improve ion conduction.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; 1922259; DMR-2011854; ACI-1053575

OSTI ID:: 1909462

Journal Information:: ACS Nano, Vol. 16, Issue 12; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (53)

Non-isothermal and isothermal cold crystallization of glass-forming chiral smectic liquid crystal (S)-4′-(1-methyloctyloxycarbonyl) biphenyl-4-yl 4-[7-(2,2,3,3,4,4,4-heptafluorobutoxy) heptyl-1-oxy]-benzoate Drzewicz, Anna; Juszyńska-Gałązka, Ewa; Zając, Wojciech Journal of Molecular Liquids, Vol. 319 https://doi.org/10.1016/j.molliq.2020.114153	journal	December 2020
Thin Film Structure of Tetraceno[2,3- b ]thiophene Characterized by Grazing Incidence X-ray Scattering and Near-Edge X-ray Absorption Fine Structure Analysis Yuan, Quan; Mannsfeld, Stefan C. B.; Tang, Ming L. Journal of the American Chemical Society, Vol. 130, Issue 11 https://doi.org/10.1021/ja0773002	journal	March 2008
Substitutional Effects on the Structural, Spectroscopic, and Photophysical Properties of Quaterthiophenes and Sexithiophenes as Well as on Their Corresponding Polyesters DiCésare, Nicolas; Belletête, Michel; Donat-Bouillud, Anne Macromolecules, Vol. 31, Issue 18 https://doi.org/10.1021/ma980397f	journal	August 1998
Liquid-crystal nanoscience: an emerging avenue of soft self-assembly Bisoyi, Hari Krishna; Kumar, Sandeep Chem. Soc. Rev., Vol. 40, Issue 1 https://doi.org/10.1039/B901793N	journal	January 2011
Anisotropic Proton-Conductive Materials Formed by the Self-Organization of Phosphonium-Type Zwitterions Ueda, Saori; Kagimoto, Junko; Ichikawa, Takahiro Advanced Materials, Vol. 23, Issue 27 https://doi.org/10.1002/adma.201100942	journal	May 2011
Discontinuous Changes in Ionic Conductivity of a Block Copolymer Electrolyte through an Order–Disorder Transition Teran, Alexander A.; Mullin, Scott A.; Hallinan, Daniel T. ACS Macro Letters, Vol. 1, Issue 2 https://doi.org/10.1021/mz200183t	journal	January 2012
Poly(ethylene oxide)-based electrolytes for lithium-ion batteries Xue, Zhigang; He, Dan; Xie, Xiaolin Journal of Materials Chemistry A, Vol. 3, Issue 38 https://doi.org/10.1039/C5TA03471J	journal	January 2015
Microsegregation: From Basic Concepts to Complexity in Liquid Crystal Self-Assembly Tschierske, Carsten Israel Journal of Chemistry, Vol. 52, Issue 10 https://doi.org/10.1002/ijch.201200053	journal	October 2012
2D assemblies of ionic liquid crystals based on imidazolium moieties: formation of ion-conductive layers Sakuda, Junji; Yoshio, Masafumi; Ichikawa, Takahiro New Journal of Chemistry, Vol. 39, Issue 6 https://doi.org/10.1039/C5NJ00085H	journal	January 2015
Effect of Plasticization on Ionic Conductivity Enhancement in Relation to Glass Transition Temperature of Crosslinked Polymer Electrolyte Membranes He, Ruixuan; Kyu, Thein Macromolecules, Vol. 49, Issue 15 https://doi.org/10.1021/acs.macromol.6b00918	journal	July 2016
Amphiphilic Cyclodextrin-Based Liquid Crystals for Proton Conduction Champagne, Pier-Luc; Ester, David; Polan, Danielle Journal of the American Chemical Society, Vol. 141, Issue 23 https://doi.org/10.1021/jacs.8b13888	journal	May 2019
Optimizing Ion Transport in Polyether-Based Electrolytes for Lithium Batteries Zheng, Qi; Pesko, Danielle M.; Savoie, Brett M. Macromolecules, Vol. 51, Issue 8 https://doi.org/10.1021/acs.macromol.7b02706	journal	April 2018
Self-assembling liquid crystals as building blocks to design nanoporous membranes suitable for molecular separations Kloos, Joey; Joosten, Niki; Schenning, Albert Journal of Membrane Science, Vol. 620 https://doi.org/10.1016/j.memsci.2020.118849	journal	February 2021
Effect of varying the composition and nanostructure of organic carbonate-containing lyotropic liquid crystal polymer electrolytes on their ionic conductivity Kerr, Robert L.; Edwards, Julian P.; Jones, Simon C. Polymer Journal, Vol. 48, Issue 5 https://doi.org/10.1038/pj.2015.119	journal	January 2016
Morphology and Thermodynamic Properties of a Copolymer with an Electronically Conducting Block: Poly(3-ethylhexylthiophene)- block -poly(ethylene oxide) Patel, Shrayesh N.; Javier, Anna E.; Beers, Keith M. Nano Letters, Vol. 12, Issue 9 https://doi.org/10.1021/nl302454c	journal	January 2012
Ionic liquid crystal with fast ion-conductive tunnels for potential application in solvent-free Li-ion batteries Yuan, Fen; Chi, Shuai; Dong, Shunping Electrochimica Acta, Vol. 294 https://doi.org/10.1016/j.electacta.2018.10.079	journal	January 2019
A conceptual review on polymer electrolytes and ion transport models Aziz, Shujahadeen B.; Woo, Thompson J.; Kadir, M. F. Z. Journal of Science: Advanced Materials and Devices, Vol. 3, Issue 1 https://doi.org/10.1016/j.jsamd.2018.01.002	journal	March 2018
Exchange Monte Carlo Method and Application to Spin Glass Simulations Hukushima, Koji; Nemoto, Koji Journal of the Physical Society of Japan, Vol. 65, Issue 6 https://doi.org/10.1143/JPSJ.65.1604	journal	June 1996
Liquid crystalline organic semiconductors for organic transistor applications Iino, Hiroaki; Hanna, Jun-ichi Polymer Journal, Vol. 49, Issue 1 https://doi.org/10.1038/pj.2016.101	journal	October 2016
Liquid-Crystalline Electrolytes for Lithium-Ion Batteries: Ordered Assemblies of a Mesogen-Containing Carbonate and a Lithium Salt Sakuda, Junji; Hosono, Eiji; Yoshio, Masafumi Advanced Functional Materials, Vol. 25, Issue 8 https://doi.org/10.1002/adfm.201402509	journal	December 2014
Li⁺ and K⁺ ionic conductivity in ionic nematic liquid crystals based on 18-diaza-crown ether substituted with six decylalkoxy-p-cyanobiphenyl chains Conejo-Rodríguez, Verónica; Cuerva, Cristián; Schmidt, Rainer Journal of Materials Chemistry C, Vol. 7, Issue 3 https://doi.org/10.1039/C8TC04898C	journal	January 2019
Zwitterionic liquid crystals as 1D and 3D lithium ion transport media Soberats, Bartolome; Yoshio, Masafumi; Ichikawa, Takahiro Journal of Materials Chemistry A, Vol. 3, Issue 21 https://doi.org/10.1039/C5TA00814J	journal	January 2015
Liquid crystals for organic thin-film transistors Iino, Hiroaki; Usui, Takayuki; Hanna, Jun-ichi Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7828	journal	April 2015
Interrogation of Electrochemical Properties of Polymer Electrolyte Thin Films with Interdigitated Electrodes Sharon, Daniel; Bennington, Peter; Liu, Claire Journal of The Electrochemical Society, Vol. 165, Issue 16 https://doi.org/10.1149/2.0291816jes	journal	January 2018
Nanostructured liquid-crystalline Li-ion conductors with high oxidation resistance: molecular design strategy towards safe and high-voltage-operation Li-ion batteries Kuwabara, Atsushi; Enomoto, Mayu; Hosono, Eiji Chemical Science, Vol. 11, Issue 39 https://doi.org/10.1039/D0SC01646B	journal	January 2020
Red/NIR‐Emissive Benzo[d]imidazole‐Cored AIEgens: Facile Molecular Design for Wavelength Extending and In Vivo Tumor Metabolic Imaging Ni, Jen‐Shyang; Zhang, Pengfei; Jiang, Tao Advanced Materials, Vol. 30, Issue 50 https://doi.org/10.1002/adma.201805220	journal	October 2018
Thin Film Structure of Triisopropylsilylethynyl-Functionalized Pentacene and Tetraceno[2,3-b]thiophene from Grazing Incidence X-Ray Diffraction Mannsfeld, Stefan C. B.; Tang, Ming Lee; Bao, Zhenan Advanced Materials, Vol. 23, Issue 1, p. 127-131 https://doi.org/10.1002/adma.201003135	journal	November 2010
Nanostructured Two-Component Liquid-Crystalline Electrolytes for High-Temperature Dye-Sensitized Solar Cells Högberg, Daniel; Soberats, Bartolome; Uchida, Satoshi Chemistry of Materials, Vol. 26, Issue 22 https://doi.org/10.1021/cm503090z	journal	November 2014
Crystal Growth, Structure, and Electronic Band Structure of α-4T Polymorphs Siegrist, Theo; Kloc, Christian; Laudise, Robert A. Advanced Materials, Vol. 10, Issue 5 https://doi.org/10.1002/(SICI)1521-4095(199803)10:5<379::AID-ADMA379>3.0.CO;2-A	journal	March 1998
Molecular Design Strategies toward Improvement of Charge Injection and Ionic Conduction in Organic Mixed Ionic–Electronic Conductors for Organic Electrochemical Transistors Kukhta, Nadzeya A.; Marks, Adam; Luscombe, Christine K. Chemical Reviews https://doi.org/10.1021/acs.chemrev.1c00266	journal	December 2021
Mesophase semiconductors in field effect transistors Shimizu, Yo; Oikawa, Kazuma; Nakayama, Ken-ichi Journal of Materials Chemistry, Vol. 17, Issue 40 https://doi.org/10.1039/b705534j	journal	January 2007
Influence of Side-Chain Chemistry on Structure and Ionic Conduction Characteristics of Polythiophene Derivatives: A Computational and Experimental Study Dong, Ban Xuan; Nowak, Christian; Onorato, Jonathan W. Chemistry of Materials, Vol. 31, Issue 4 https://doi.org/10.1021/acs.chemmater.8b05257	journal	February 2019
Side chain engineering control of mixed conduction in oligoethylene glycol-substituted polythiophenes Onorato, Jonathan W.; Wang, Zhongyang; Sun, Yangyang Journal of Materials Chemistry A, Vol. 9, Issue 37 https://doi.org/10.1039/D1TA05379E	journal	January 2021
A series of new conjugated oligothiophenes for organic electronics Feroci, Marta; Civitarese, Tommaso; Pandolfi, Fabiana AIP Conference Proceedings https://doi.org/10.1063/5.0023648	conference	January 2020
3D Continuous Water Nanosheet as a Gyroid Minimal Surface Formed by Bicontinuous Cubic Liquid-Crystalline Zwitterions Ichikawa, Takahiro; Kato, Takashi; Ohno, Hiroyuki Journal of the American Chemical Society, Vol. 134, Issue 28 https://doi.org/10.1021/ja304124w	journal	July 2012
Synthesis of thieno[3,2-b]thiophene derived conjugated oligomers for field-effect transistors applications Tang, Weihua; Singh, Samarendra P.; Ong, Kok Haw Journal of Materials Chemistry, Vol. 20, Issue 8 https://doi.org/10.1039/b920112b	journal	January 2010
Thienothiophenes, Dithienothiophenes, and Thienoacenes: Syntheses, Oligomers, Polymers, and Properties Cinar, Mehmet Emin; Ozturk, Turan Chemical Reviews, Vol. 115, Issue 9 https://doi.org/10.1021/cr500271a	journal	April 2015
Structure and ionic conductive properties of polydioxolane-polyurethane-based electrolytes Zhu, Weihua; Yang, Bing; Wang, Xinling Journal of Applied Polymer Science, Vol. 83, Issue 1 https://doi.org/10.1002/app.10041	journal	November 2001
Self-Assembly Behavior of an Oligothiophene-Based Conjugated Liquid Crystal and Its Implication for Ionic Conductivity Characteristics Liu, Ziwei; Dong, Ban Xuan; Misra, Mayank Advanced Functional Materials, Vol. 29, Issue 2 https://doi.org/10.1002/adfm.201805220	journal	November 2018
Intrinsic Ion Transport Properties of Block Copolymer Electrolytes Sharon, Daniel; Bennington, Peter; Dolejsi, Moshe ACS Nano, Vol. 14, Issue 7 https://doi.org/10.1021/acsnano.0c03713	journal	June 2020
Structure Control of a π-Conjugated Oligothiophene-Based Liquid Crystal for Enhanced Mixed Ion/Electron Transport Characteristics Dong, Ban Xuan; Liu, Ziwei; Misra, Mayank ACS Nano, Vol. 13, Issue 7 https://doi.org/10.1021/acsnano.9b01055	journal	June 2019
Gemini Thermotropic Smectic Liquid Crystals for Two-Dimensional Nanostructured Water-Treatment Membranes Hamaguchi, Kazuma; Ichikawa, Rino; Kajiyama, Satoshi ACS Applied Materials & Interfaces, Vol. 13, Issue 17 https://doi.org/10.1021/acsami.0c20524	journal	April 2021
GIXSGUI : a MATLAB toolbox for grazing-incidence X-ray scattering data visualization and reduction, and indexing of buried three-dimensional periodic nanostructured films Jiang, Zhang Journal of Applied Crystallography, Vol. 48, Issue 3 https://doi.org/10.1107/S1600576715004434	journal	April 2015
π-Conjugated molecules with fused rings for organic field-effect transistors: design, synthesis and applications Wu, Weiping; Liu, Yunqi; Zhu, Daoben Chem. Soc. Rev., Vol. 39, Issue 5 https://doi.org/10.1039/B813123F	journal	January 2010
Structural order in conjugated oligothiophenes and its implications on opto-electronic devices Fichou, Denis Journal of Materials Chemistry, Vol. 10, Issue 3 https://doi.org/10.1039/a908312j	journal	January 2000
Diffusion and ionic conductivity in Li(CF3SO3)PEG10 and LiN(CF3SO2)2PEG10 Johansson, A.; Gogoll, A.; Tegenfeldt, J. Polymer, Vol. 37, Issue 8 https://doi.org/10.1016/0032-3861(96)81136-0	journal	April 1996
Gwyddion: an open-source software for SPM data analysis Nečas, David; Klapetek, Petr Open Physics, Vol. 10, Issue 1 https://doi.org/10.2478/s11534-011-0096-2	journal	January 2012
Liquid-Crystalline Dye-Sensitized Solar Cells: Design of Two-Dimensional Molecular Assemblies for Efficient Ion Transport and Thermal Stability Högberg, Daniel; Soberats, Bartolome; Yatagai, Ryo Chemistry of Materials, Vol. 28, Issue 18 https://doi.org/10.1021/acs.chemmater.6b01590	journal	July 2016
Comprehensive picture of $p$ -type doping of P3HT with the molecular acceptor F $_{4}$ TCNQ Pingel, P.; Neher, D. Physical Review B, Vol. 87, Issue 11 https://doi.org/10.1103/PhysRevB.87.115209	journal	March 2013
Simultaneous Electronic and Ionic Conduction in a Block Copolymer: Application in Lithium Battery Electrodes Javier, Anna E.; Patel, Shrayesh N.; Hallinan, Daniel T. Angewandte Chemie International Edition, Vol. 50, Issue 42 https://doi.org/10.1002/anie.201102953	journal	September 2011
Optimization by Simulated Annealing Kirkpatrick, S.; Gelatt, C. D.; Vecchi, M. P. Science, Vol. 220, Issue 4598 https://doi.org/10.1126/science.220.4598.671	journal	May 1983
Polymer Crystallinity Controls Water Uptake in Glycol Side-Chain Polymer Organic Electrochemical Transistors Flagg, Lucas Q.; Bischak, Connor G.; Onorato, Jonathan W. Journal of the American Chemical Society, Vol. 141, Issue 10 https://doi.org/10.1021/jacs.8b12640	journal	February 2019
Microstructure of Oligofluorene Asymmetric Derivatives in Organic Thin Film Transistors Yuan, Quan; Mannsfeld, Stefan C. B.; Tang, Ming L. Chemistry of Materials, Vol. 20, Issue 8 https://doi.org/10.1021/cm800071r	journal	April 2008

Similar Records

X-Ray Scattering Study of Thin Films of Poly(2,5-Bis(3-Alkylthiophen-2-Yl)Thieno[3,2-B]thiophene)

Journal Article · Tue Jun 02 00:00:00 EDT 2009 · J.Am.Chem.Soc.129:3226-3237,2007 · OSTI ID:1909462

Chabinyc, M L; Toney, M F; Kline, R J; +2 more

Coherent Dynamics of Mixed Frenkel and Charge-Transfer Excitons in Dinaphtho[2,3- b :2'3'- f ]thieno[3,2- b ]-thiophene Thin Films: The Importance of Hole Delocalization

Journal Article · Thu Mar 24 00:00:00 EDT 2016 · Journal of Physical Chemistry Letters · OSTI ID:1909462

Fujita, Takatoshi; Atahan-Evrenk, Sule; Sawaya, Nicolas P. D.; +1 more

Synthesis and photovoltaic properties of new thieno[3,2-b]indole-based dyes

Journal Article · Sat Jun 15 00:00:00 EDT 2019 · Russian Chemical Bulletin · OSTI ID:1909462

Steparuk, A. S.; Irgashev, R. A.; Rusinov, G. L.; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ion conduction
π-conjugated liquid crystal
molecular dynamics simulation
thin film electrochemical impedance spectroscopy
X-ray diffraction pattern

Title: Ion Transport in 2D Nanostructured $$\pi$$-Conjugated Thieno[3,2-b]thiophene-Based Liquid Crystal

Citation Formats

References (53)

Similar Records

Related Subjects