ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img
RETURN TO ISSUEPREVResearch ArticleNEXT

Constructing Alternated Heterobimetallic [Fe(II)/Os(II)] Supramolecular Polymers with Diverse Solubility for Facile Fabrication of Voltage-Tunable Multicolor Electrochromic Devices

  • Manas Kumar Bera
    Manas Kumar Bera
    Electronic Functional Macromolecules Group, Research Center for Functional Materials, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
  • Yoshikazu Ninomiya
    Yoshikazu Ninomiya
    Electronic Functional Macromolecules Group, Research Center for Functional Materials, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
  • , and 
  • Masayoshi Higuchi*
    Masayoshi Higuchi
    Electronic Functional Macromolecules Group, Research Center for Functional Materials, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
    *Email: [email protected] (M.H.).
Cite this: ACS Appl. Mater. Interfaces 2020, 12, 12, 14376–14385
Publication Date (Web):March 9, 2020
https://doi.org/10.1021/acsami.9b21966
Copyright © 2020 American Chemical Society

    Article Views

    1879

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (1)»

    Abstract

    Abstract Image

    Metallo-supramolecular polymer (MSP)-based electrochromic devices (ECDs) have drawn much attention because of their variable colors and attractive electrochromic (EC) properties. However, fabrication of voltage-tunable multicolor ECDs using single MSP is yet hard to realize. We anticipated alternate introduction of two different redox-active metal ions in an MSP combined with the adjustment of counteranions could be a solution to fabricate multicolor ECDs. The heterometals will induce color variability upon voltage alteration, and counteranions will help to tune the solubility of MSP in different solvents. In an attempt to fulfill this target, we have synthesized four heterobimetallic supramolecular polymers (HBPs) having different counteranions (BF4, Cl, PF6, and OAc), in which Fe(II) and Os(II) are alternately complexed by two terpyridine units. To apply as EC material, the HBPs should be soluble in methanol and insoluble in acetonitrile for the preparation of EC film as well as ECDs. However, among the HBPs, only HBP-OAc is found to meet this requirement. The EC behaviors of the spray-coating film of HBP-OAc on an indium tin oxide (ITO)-coated glass substrate are investigated in terms of maximum transmittance contrast, coloration voltage, response time, coloration efficiency, and operational stability, which exhibits reversible multicolor electrochromism (the initial purple color of the film is changed to violet followed by greenish-yellow) upon alteration of the voltage from 0.0 to 0.7 V [required to oxidize the Os(II) ion] and to 1.0 V [required to oxidize the Fe(II) ion]. The film is also integrated into a laminated ECD by using lithium-based gel electrolyte. Finally, as a proof-of-concept, a prototype voltage-tunable multicolor EC display (6 cm × 2.5 cm) is fabricated by using a designed image containing a flower, leaves, and a flower pot, which exhibits six different types of multicolor image upon application of tunable voltages.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.9b21966.

    • Materials, characterization details, device fabrication process, and additional experimental data (NMR, UV, CV, and XPS) (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 37 publications.

    1. Sanjib Sarmah, Siddhartha Shankar Kashyap, Manas Kumar Bera. Dual Redox-Responsive Os/Ru-Based Alternated Heterobimetallic Supramolecular Polymer as a Multicolor Electrochromic Material for Camouflage Devices. ACS Applied Electronic Materials 2023, 5 (3) , 1738-1749. https://doi.org/10.1021/acsaelm.2c01765
    2. Binrui Li, Shaojian Zhang, Peng Liao, Peng Liu, Zhihang Ye, Chongxuan Liu. NOM-Induced Dissolution of CrxFe1–x(OH)3 Precipitates and Formation of Cr(III)-NOM-Fe Colloids under Oxic and Anoxic Conditions. ACS Earth and Space Chemistry 2022, 6 (12) , 2995-3006. https://doi.org/10.1021/acsearthspacechem.2c00255
    3. Chang Gu, Ai-Bo Jia, Yu-Mo Zhang, Sean Xiao-An Zhang. Emerging Electrochromic Materials and Devices for Future Displays. Chemical Reviews 2022, 122 (18) , 14679-14721. https://doi.org/10.1021/acs.chemrev.1c01055
    4. Yemineni S. L. V. Narayana, Sanjoy Mondal, Utpal Rana, Yoshikazu Ninomiya, Dines Chandra Santra, Takefumi Yoshida, Masayoshi Higuchi. One-Step Synthesis of a Three-Dimensionally Hyperbranched Fe(II)-Based Metallo-Supramolecular Polymer Using an Asymmetrical Ditopic Ligand for Durable Electrochromic Films with Wide Absorption, Large Optical Contrast, and High Coloration Efficiency. ACS Applied Electronic Materials 2021, 3 (5) , 2044-2055. https://doi.org/10.1021/acsaelm.1c00061
    5. Nadia O. Laschuk, Iraklii I. Ebralidze, E. Bradley Easton, Olena V. Zenkina. Systematic Design of Electrochromic Energy Storage Devices Based on Metal–Organic Monolayers. ACS Applied Energy Materials 2021, 4 (4) , 3469-3479. https://doi.org/10.1021/acsaem.0c03218
    6. Indulekha Mukkatt, Anjali Nirmala, Nayan Dev Madhavan, Sreejith Shankar, Biswapriya Deb, Ayyappanpillai Ajayaghosh. Ligand-Controlled Electrochromic Diversification with Multilayer Coated Metallosupramolecular Polymer Assemblies. ACS Applied Materials & Interfaces 2021, 13 (4) , 5245-5255. https://doi.org/10.1021/acsami.0c20428
    7. Sanjoy Mondal, Dines Chandra Santra, Yoshikazu Ninomiya, Takefumi Yoshida, Masayoshi Higuchi. Dual-Redox System of Metallo-Supramolecular Polymers for Visible-to-Near-IR Modulable Electrochromism and Durable Device Fabrication. ACS Applied Materials & Interfaces 2020, 12 (52) , 58277-58286. https://doi.org/10.1021/acsami.0c18109
    8. Yemineni S. L. V. Narayana, Utpal Rana, Chanchal Chakraborty, Takefumi Yoshida, Masayoshi Higuchi. One-Pot Synthesis of Three-Dimensionally Hyperbranched Eu/Fe-Based Heterometallo-Supramolecular Polymers as Thermally Tough Proton-Conducting Nanoparticles. ACS Applied Polymer Materials 2020, 2 (11) , 4439-4448. https://doi.org/10.1021/acsapm.0c00541
    9. Md. Delwar Hossain, Chanchal Chakraborty, Utpal Rana, Sanjoy Mondal, Hans-Jürgen Holdt, Masayoshi Higuchi. Green-to-Black Electrochromic Copper(I)-Based Metallo-Supramolecular Polymer with a Perpendicularly Twisted Structure. ACS Applied Polymer Materials 2020, 2 (11) , 4449-4454. https://doi.org/10.1021/acsapm.0c00559
    10. Nadia O. Laschuk, Rana Ahmad, Iraklii I. Ebralidze, Jade Poisson, E. Bradley Easton, Olena V. Zenkina. Multichromic Monolayer Terpyridine-Based Electrochromic Materials. ACS Applied Materials & Interfaces 2020, 12 (37) , 41749-41757. https://doi.org/10.1021/acsami.0c11478
    11. Utpal Rana, Dines Chandra Santra, Banchhanidhi Prusti, Chanchal Chakraborty, Taichi Ikeda, Yuko Saito, Kazuhiko Takeuchi, Ritsuko Nagahata, Masayoshi Higuchi. Microwave‐Assisted Quick Synthesis of Ru(II)‐Based Metallosupramolecular Polymer for Improved Electrochromic Properties. Macromolecular Chemistry and Physics 2024, 225 (5) https://doi.org/10.1002/macp.202300381
    12. Pooja V. Chavan, Pramod V. Rathod, Hern Kim. Vis‐NIR Modulation in a Dynamically Reversible Single C‐pBPV Biopolymer Electrolyte for Sustainable Systems in Electrochromism. Advanced Optical Materials 2024, https://doi.org/10.1002/adom.202302976
    13. Fangfei Liu, Xiong Liu, Tursun Abdiryim, Haibin Gu, Didier Astruc. Heterometallic macromolecules: Synthesis, properties and multiple nanomaterial applications. Coordination Chemistry Reviews 2024, 500 , 215544. https://doi.org/10.1016/j.ccr.2023.215544
    14. Manas Kumar Bera, Sanjib Sarmah, Dines Chandra Santra, Masayoshi Higuchi. Heterometallic supramolecular polymers: From synthesis to properties and applications. Coordination Chemistry Reviews 2024, 501 , 215573. https://doi.org/10.1016/j.ccr.2023.215573
    15. Sonal Sharma, Anil Kumar, Deepa Oberoi, Samaresh Ghosh, Jagannath Majhi, Kumari Priya, Anasuya Bandyopadhyay. A review on diverse applications of electrochemically active functional metallopolymers. Reactive and Functional Polymers 2023, 193 , 105742. https://doi.org/10.1016/j.reactfunctpolym.2023.105742
    16. Nadia O. Laschuk, Iraklii I. Ebralidze, Olena V. Zenkina. Polypyridine-based architectures for smart electrochromic and energy storage materials. Canadian Journal of Chemistry 2023, 101 (7) , 400-417. https://doi.org/10.1139/cjc-2022-0268
    17. Sayan Halder, Chanchal Chakraborty. Fe(II)-based dual function metallo-supramolecular polymer with thiazolothiazole spacer for high-performance electrochromic supercapattery. Solar Energy Materials and Solar Cells 2023, 254 , 112288. https://doi.org/10.1016/j.solmat.2023.112288
    18. Shiyou Liu, Congyuan Wei, Han Wang, Weilong Yang, Jian Zhang, Zhuanpei Wang, Weili Zhao, Pooi See Lee, Guofa Cai. Processable nanoarchitectonics of two-dimensional metallo-supramolecular polymer for electrochromic energy storage devices with high coloration efficiency and stability. Nano Energy 2023, 110 , 108337. https://doi.org/10.1016/j.nanoen.2023.108337
    19. Wenzhi Zhang, Chen Zhang, Jianchang Liu, Xiao Wang, Shengbo Zhu. Fabrication of nanostructured polythiophene derivative films and their applications in large-size electrochromic devices. Solar Energy Materials and Solar Cells 2023, 251 , 112146. https://doi.org/10.1016/j.solmat.2022.112146
    20. Abdul Awal, Md. Mithu Mia, Shifa Sarkar, Santa Islam, Sohag Sarker, S. M. Abu Nayem, Md. Delwar Hossain, A. J. Saleh Ahammad. Fe(II)-Based Metallo-Supramolecular Polymer Film for Electrochemical Detection of Nitrite: Studies of Kinetics and Reaction Mechanisms. Journal of The Electrochemical Society 2023, 170 (3) , 037508. https://doi.org/10.1149/1945-7111/acc01a
    21. Satya Ranjan Jena, Tanmoy Mandal, Joyanta Choudhury. Metal‐Terpyridine Assembled Functional Materials for Electrochromic, Catalytic and Environmental Applications. The Chemical Record 2022, 22 (12) https://doi.org/10.1002/tcr.202200165
    22. Zi-Jie Gong, Yemineni S.L.V. Narayana, Yen-Chun Lin, Wei-Hsiang Huang, Wei-Nien Su, Yi-Pei Li, Masayoshi Higuchi, Wen-Yueh Yu. Rational synthesis of ruthenium-based metallo-supramolecular polymers as heterogeneous catalysts for catalytic transfer hydrogenation of carbonyl compounds. Applied Catalysis B: Environmental 2022, 312 , 121383. https://doi.org/10.1016/j.apcatb.2022.121383
    23. Min Liu, Keke Shi, Zhongyao Duan, Mei Zhang, You Xu, Ziqiang Wang, Xiaonian Li, Liang Wang, Hongjing Wang. P-modified hollow carbon mesoporous nanospheres decorated with ultrafine OsP alloy nanoparticles for nonacidic hydrogen evolution. Journal of Materials Chemistry A 2022, 10 (24) , 13042-13047. https://doi.org/10.1039/D2TA02161G
    24. Masayoshi Higuchi. Electrochromic Coordination Polymers. Bulletin of Japan Society of Coordination Chemistry 2022, 79 (0) , 68-77. https://doi.org/10.4019/bjscc.79.68
    25. Manas Kumar Bera, Sudhanya Mohanty, Siddhartha Shankar Kashyap, Sanjib Sarmah. Electrochromic coordination nanosheets: Achievements and future perspective. Coordination Chemistry Reviews 2022, 454 , 214353. https://doi.org/10.1016/j.ccr.2021.214353
    26. Manas Kumar Bera, Yoshikazu Ninomiya, Masayoshi Higuchi. Stepwise introduction of three different transition metals in metallo-supramolecular polymer for quad-color electrochromism. Communications Chemistry 2021, 4 (1) https://doi.org/10.1038/s42004-021-00495-1
    27. Mohammad Amin Farahmand Nejad, Saba Ranjbar, Claudio Parolo, Emily P. Nguyen, Ruslan Álvarez-Diduk, Mohammad Reza Hormozi-Nezhad, Arben Merkoçi. Electrochromism: An emerging and promising approach in (bio)sensing technology. Materials Today 2021, 50 , 476-498. https://doi.org/10.1016/j.mattod.2021.06.015
    28. Nadia O. Laschuk, Iraklii I. Ebralidze, E. Bradley Easton, Olena V. Zenkina. Osmium‐ and Cobalt‐Terpyridine‐Based Electrochromic Devices for “Smart” Signage Application: The Effect of Lighting on Color Perception. Advanced Electronic Materials 2021, 7 (10) https://doi.org/10.1002/aelm.202100460
    29. Mira T. Rupp, Thomas Auvray, Garry S. Hanan, Dirk G. Kurth. Electrochemical and Photophysical Study of Homoleptic and Heteroleptic Methylated Ru(II) Bis‐terpyridine Complexes. European Journal of Inorganic Chemistry 2021, 2021 (28) , 2822-2829. https://doi.org/10.1002/ejic.202100092
    30. Shiyou Liu, Ping Zhang, Jianjian Fu, Congyuan Wei, Guofa Cai. A Mini-Review: Pyridyl-Based Coordination Polymers for Energy Efficient Electrochromic Application. Frontiers in Energy Research 2021, 9 https://doi.org/10.3389/fenrg.2021.620203
    31. . Supramolecular Polymers, Based on Metal‐to‐Ligand Interactions*. 2021, 117-194. https://doi.org/10.1002/9783527685325.ch4
    32. Nadia O. Laschuk, Rana Ahmad, Iraklii I. Ebralidze, Jade Poisson, Franco Gaspari, E. Bradley Easton, Olena V. Zenkina. Multiple electrochemically accessible colour states in surface-confined metal–organic monolayers: stepwise embedding of individual metal centres. Materials Advances 2021, 2 (3) , 953-962. https://doi.org/10.1039/D0MA00735H
    33. Wenzhi Zhang, Xianghong Chen, Xiao Wang, Shengbo Zhu, Sumin Wang, Qiguan Wang. Pulsed electrodeposition of nanostructured polythiothene film for high-performance electrochromic devices. Solar Energy Materials and Solar Cells 2021, 219 , 110775. https://doi.org/10.1016/j.solmat.2020.110775
    34. Masayoshi Higuchi, Yukio Fujii, Yoji Hisamatsu. [Paper] Designed Electrochromic Display Devices with Ru(II)-Based Metallo-Supramolecular Polymer For Experience-Based Exhibits at Ehime Prefectural Science Museum. ITE Transactions on Media Technology and Applications 2021, 9 (4) , 228-233. https://doi.org/10.3169/mta.9.228
    35. Manas Kumar Bera, Yoshikazu Ninomiya, Masayoshi Higuchi. Synthesis of an Alternated Heterobimetallic Supramolecular Polymer Based on Ru(II) and Fe(II). Molecules 2020, 25 (22) , 5261. https://doi.org/10.3390/molecules25225261
    36. Naveen Malik, Michal Lahav, Milko E. van der Boom. Electrochromic Metallo–Organic Nanoscale Films: A Molecular Mix and Match Approach to Thermally Robust and Multistate Solid‐State Devices. Advanced Electronic Materials 2020, 6 (10) https://doi.org/10.1002/aelm.202000407
    37. Ofir Eisenberg, Yadid M. Algavi, Haim Weissman, Julia Narevicius, Boris Rybtchinski, Michal Lahav, Milko E. van der Boom. Dual Function Metallo–Organic Assemblies for Electrochromic–Hybrid Supercapacitors. Advanced Materials Interfaces 2020, 7 (16) https://doi.org/10.1002/admi.202000718

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect