ACS Publications. Most Trusted. Most Cited. Most Read
Electronic Structure and Properties of Poly- and Oligoazulenes

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Phys. Chem. C 2008, 112, 6, 2156-2164
    Article

    Electronic Structure and Properties of Poly- and Oligoazulenes
    Click to copy article linkArticle link copied!

    View Author Information
    Department of Analytical Chemistry, Lund University, P.O. Box 124, SE-221 00 Lund, Sweden, Institut für Organische Chemie, Universität Regensburg, Universitätsstrasse 31, D-93053 Regensburg, Germany, and Institut für Organische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany
    Other Access OptionsSupporting Information (1)

    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2008, 112, 6, 2156–2164
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jp074376b
    Published January 17, 2008
    Copyright © 2008 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!

    One of the most important research interests in the field of organic photovoltaic devices (OPVs) is the development of new materials which can serve as light-absorbing electron donors and hole-conducting (p-type) semiconductors. In this context, 1,3-polyazulenes were synthesized chemically and electrochemically. Their spectroscopic and electrochemical properties are compared with those of the 1,3-oligoazulenes Az1−Az6. The UV−vis spectra of the neutral azulenes Az1−Az6 show a linear correlation between the lowest absorption maximum and the inverse chain length 1/n leading to a band gap of Eg = 1.90 eV for infinite chain length. Derived from this correlation the effective conjugation length of chemically synthesized polyazulene is only about 10. By an alternative approach, a band gap of Eg = 1.46 eV was determined. Depending on the applied potential the oligomers Az2−Az6 undergo up to two reversible oxidation processes or further polymerization which results in the formation of polymer films at the electrode. The potentiodynamic oxidation of chemically synthesized polyazulene leads to electrocrystallization at the electrode, whereas films of polyazulenes are obtained directly upon oxidation of Az1−Az6. Chemically and electrochemically generated polyazulenes adsorbed on Pt show similar electrochemical behavior upon positive doping. The spectroelectrochemical investigations in combination with density functional theory (DFT) calculations lead to the conclusion that polyazulene can be oxidized up to a doping level of one charge per three or four azulene units. At this stage polarons or polaron pairs are formed (depending on the doping level) but not bipolarons. At higher doping levels the polymers start to decompose.

    Copyright © 2008 American Chemical Society

    Subjects

    what are subjects

    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. Add or change your institution or let them know you’d like them to include access.

    *

     Corresponding author. Phone:  +46 46 222 0103. Fax:  +46 46 222 4544. E-mail:  [email protected].

    †

     Lund University.

    ‡

     Universität Regensburg.

    §

     Julius-Maximilians-Universität Würzburg.

    Supporting Information Available

    Click to copy section linkSection link copied!

    The experimental part (details about synthesis, electrochemical setup, and DFT calculations), additional CV experiments (comparison between azulene and chemically and electrochemically synthesized polyazulene), the spectroelectrochemistry of films of PAz2 and PAz3 in monomer-free solution, and the bond distances and dihedral angles for neutral Az8. This material is available free of charge via the Internet at http://pubs.acs.org.

    Terms & Conditions

    Electronic Supporting Information files are available without a subscription to ACS Web Editions. The American Chemical Society holds a copyright ownership interest in any copyrightable Supporting Information. Files available from the ACS website may be downloaded for personal use only. Users are not otherwise permitted to reproduce, republish, redistribute, or sell any Supporting Information from the ACS website, either in whole or in part, in either machine-readable form or any other form without permission from the American Chemical Society. For permission to reproduce, republish and redistribute this material, requesters must process their own requests via the RightsLink permission system. Information about how to use the RightsLink permission system can be found at http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 27 publications.

    1. Rahul Yewale, Pia Damlin, Carita Kvarnström. Effect of Oxidants on Properties of Electroactive Ultrathin Polyazulene Films Synthesized by Vapor Phase Polymerization at Atmospheric Pressure. Langmuir 2022, 38 (49) , 15165-15177. https://doi.org/10.1021/acs.langmuir.2c02215
    2. Yusuke Shibuya, Kazuhiro Aonuma, Tomohiro Kimura, Takuro Kaneko, Wataru Fujiwara, Yuji Yamaguchi, Daisuke Kumaki, Shizuo Tokito, Hiroshi Katagiri. Linear Biazulene Isomers: Effects of Molecular and Packing Structure on Optoelectronic and Charge-Transport Properties. The Journal of Physical Chemistry C 2020, 124 (8) , 4738-4746. https://doi.org/10.1021/acs.jpcc.9b11214
    3. Tao Tang, Tingting Lin, FuKe Wang, and Chaobin He . Origin of Near-Infrared Absorption for Azulene-Containing Conjugated Polymers upon Protonation or Oxidation. The Journal of Physical Chemistry B 2015, 119 (25) , 8176-8183. https://doi.org/10.1021/acs.jpcb.5b01613
    4. Rose-Marie Latonen, Anna Österholm, Carita Kvarnström, and Ari Ivaska . Electrochemical and Spectroelectrochemical Study of Polyazulene/BBL-PEO Donor–Acceptor Composite Layers. The Journal of Physical Chemistry C 2012, 116 (44) , 23793-23802. https://doi.org/10.1021/jp308420s
    5. Gilbert Nöll, Jörg Daub, Michaela Lutz, and Knut Rurack . Synthesis, Spectroscopic Properties, and Electropolymerization of Azulene Dyads. The Journal of Organic Chemistry 2011, 76 (12) , 4859-4873. https://doi.org/10.1021/jo200080v
    6. Anna Österholm, Andreas Petr, Carita Kvarnström, Ari Ivaska and Lothar Dunsch. The Nature of the Charge Carriers in Polyazulene as Studied by in Situ Electron Spin Resonance−UV−Visible−Near-Infrared Spectroscopy. The Journal of Physical Chemistry B 2008, 112 (45) , 14149-14157. https://doi.org/10.1021/jp805813s
    7. Anamaria Hanganu, Catalin Maxim, Andreea Dogaru, Adrian E. Ion, Coralia Bleotu, Augustin M. Madalan, Daniela Bala, Simona Nica. Synthesis, Physicochemical Properties, and Ion Recognition Ability of Azulene-Based Bis-(Thio)Semicarbazone. Molecules 2025, 30 (1) , 83. https://doi.org/10.3390/molecules30010083
    8. Takahiro Tsuchiya, Makoto Higashibeppu, Yasuhiro Mazaki. Synthesis and Properties of Twisted and Helical Azulene Oligomers and Azulene‐Based Polycyclic Hydrocarbons. ChemistryOpen 2023, 12 (11) https://doi.org/10.1002/open.202100298
    9. Cristian Pirvu, Gabriela Stanciu, George-Octavian Buica. Cu( ii ) and Hg( ii ) detection under photo-assisted accumulation in an open circuit potential at a polyazulene–EDTA like modified electrode. The Analyst 2022, 147 (21) , 4730-4734. https://doi.org/10.1039/D2AN01333A
    10. Rahul Yewale, Pia Damlin, Milla Suominen, Carita Kvarnström. Fabrication of electroactive multi-layered polyazulene thin films by atmospheric pressure-vapor phase polymerization. Materials Chemistry and Physics 2022, 275 , 125292. https://doi.org/10.1016/j.matchemphys.2021.125292
    11. Jiaqian Huang, Senhe Huang, Yazhen Zhao, Boxu Feng, Kaiyue Jiang, Sai Sun, Changchun Ke, Emmanuel Kymakis, Xiaodong Zhuang. Azulene‐Based Molecules, Polymers, and Frameworks for Optoelectronic and Energy Applications. Small Methods 2020, 4 (10) https://doi.org/10.1002/smtd.202000628
    12. Qiang Sun, Ian Cheng-Yi Hou, Kristjan Eimre, Carlo A. Pignedoli, Pascal Ruffieux, Akimitsu Narita, Roman Fasel. On-surface synthesis of polyazulene with 2,6-connectivity. Chemical Communications 2019, 55 (89) , 13466-13469. https://doi.org/10.1039/C9CC07168G
    13. Takahiro Tsuchiya, Yuka Katsuoka, Kenji Yoza, Hiroyasu Sato, Yasuhiro Mazaki. Stereochemistry, Stereodynamics, and Redox and Complexation Behaviors of 2,2′‐Diaryl‐1,1′‐Biazulenes. ChemPlusChem 2019, 84 (11) , 1659-1667. https://doi.org/10.1002/cplu.201900262
    14. Ronald P. Steer. Photophysics of molecules containing multiples of the azulene carbon framework. Journal of Photochemistry and Photobiology C: Photochemistry Reviews 2019, 40 , 68-80. https://doi.org/10.1016/j.jphotochemrev.2019.06.002
    15. Emilia Grądzka, Patrycja Makowska, Krzysztof Winkler. Chemically formed conducting polyazulene: From micro- to nanostructures. Synthetic Metals 2018, 246 , 115-121. https://doi.org/10.1016/j.synthmet.2018.10.002
    16. Milla Suominen, Pia Damlin, Carita Kvarnström. Probing the interactions in composite of graphene oxide and polyazulene in ionic liquid by in situ spectroelectrochemistry. Electrochimica Acta 2018, 284 , 168-176. https://doi.org/10.1016/j.electacta.2018.07.069
    17. Milla Suominen, Pia Damlin, Sari Granroth, Carita Kvarnström. Improved long term cycling of polyazulene/reduced graphene oxide composites fabricated in a choline based ionic liquid. Carbon 2018, 128 , 205-214. https://doi.org/10.1016/j.carbon.2017.11.083
    18. Milla Suominen, Suvi Lehtimäki, Rahul Yewale, Pia Damlin, Sampo Tuukkanen, Carita Kvarnström. Electropolymerized polyazulene as active material in flexible supercapacitors. Journal of Power Sources 2017, 356 , 181-190. https://doi.org/10.1016/j.jpowsour.2017.04.082
    19. Kazuhiko Tsurui, Masahito Murai, Sung‐Yu Ku, Craig J. Hawker, Maxwell J. Robb. Modulating the Properties of Azulene‐Containing Polymers through Controlled Incorporation of Regioisomers. Advanced Functional Materials 2014, 24 (46) , 7338-7347. https://doi.org/10.1002/adfm.201402554
    20. Masahito Murai, Sung-Yu Ku, Neil D. Treat, Maxwell J. Robb, Michael L. Chabinyc, Craig J. Hawker. Modulating structure and properties in organic chromophores: influence of azulene as a building block. Chem. Sci. 2014, 5 (10) , 3753-3760. https://doi.org/10.1039/C4SC01623H
    21. Eugenia Andreea Dragu, Simona Nica, Victorita Tecuceanu, Daniela Bala, Constantin Mihailciuc, Anamaria Hanganu, Alexandru C. Razus. Synthesis and Electrochemical Properties of Carbocyclic and Heterocyclic Diazulenylethenes. European Journal of Organic Chemistry 2013, 2013 (29) , 6601-6610. https://doi.org/10.1002/ejoc.201300354
    22. Eugenia Andreea Dragu, Simona Nica, Matei Raicopol, Adriana Baran, Dan-Florin Anghel, Bogdan Cojocaru, Laszlo Tarko, Alexandru C. Razus. Synthesis, solid-state photophysical properties and electropolymerization of novel diazulenyl ethenes. Tetrahedron Letters 2012, 53 (21) , 2611-2614. https://doi.org/10.1016/j.tetlet.2012.03.044
    23. Masahito Murai, Elizabeth Amir, Roey J. Amir, Craig J. Hawker. Azulene-based conjugated polymers: unique seven-membered ring connectivity leading to stimuli-responsiveness. Chemical Science 2012, 3 (9) , 2721. https://doi.org/10.1039/c2sc20615c
    24. Eleonora-Mihaela Ungureanu, George-Octavian Buica, Alexandru Razus, Liviu Birzan, Elena Diana Giol. Study on 5-(azulen-1-ylmethylene)-2,2-dimethyl-1,3-dioxane-4,6-diones by electrochemical methods. Monatshefte für Chemie - Chemical Monthly 2011, 142 (3) , 243-250. https://doi.org/10.1007/s00706-011-0445-2
    25. Heinz Bässler, Anna Köhler. Charge Transport in Organic Semiconductors. 2011, 1-65. https://doi.org/10.1007/128_2011_218
    26. Anna Österholm, Carita Kvarnström, Ari Ivaska. Ionic liquids in electrosynthesis and characterization of a polyazulene-fullerene composite. Electrochimica Acta 2011, 56 (3) , 1490-1497. https://doi.org/10.1016/j.electacta.2010.09.089
    27. Rose-Marie Latonen, Carita Kvarnström, Ari Ivaska. Electrochemical preparation of oligo(azulene) on nanoporous TiO2 and characterization of the composite layer. Journal of Applied Electrochemistry 2010, 40 (9) , 1583-1591. https://doi.org/10.1007/s10800-010-0143-5
    Download PDF
    Go to The Journal of Physical Chemistry C
    Get e-Alerts
    Get e-Alerts

    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2008, 112, 6, 2156–2164
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jp074376b
    Published January 17, 2008
    Copyright © 2008 American Chemical Society
    Request reuse permissions

    Article Views

    1251

    Altmetric

    -

    Citations

    27
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.