Viologen-Based Conjugated Covalent Organic Networks via Zincke Reaction

Gobinda Das, Tina Skorjanc, Sudhir Kumar Sharma, Felipe Gándara, Matteo Lusi, D. S. Shankar Rao, Sridurai Vimala, Subbarao Krishna Prasad, Jesus Raya, Dong Suk Han, Ramesh Jagannathan, John Carl Olsen, Ali Trabolsi

    Research output: Contribution to journalArticle

    Abstract

    Morphology influences the functionality of covalent organic networks and determines potential applications. Here, we report for the first time the use of Zincke reaction to fabricate, under either solvothermal or microwave conditions, a viologen-linked covalent organic network in the form of hollow particles or nanosheets. The synthesized materials are stable in acidic, neutral, and basic aqueous solutions. Under basic conditions, the neutral network assumes radical cationic character without decomposing or changing structure. Solvent polarity and heating method determine product morphology. Depending upon solvent polarity, the resulting polymeric network forms either uniform self-templated hollow spheres (HS) or hollow tubes (HT). The spheres develop via an inside-out Ostwald ripening mechanism. Interestingly, microwave conditions and certain solvent polarities result in the formation of a robust covalent organic gel framework (COGF) that is organized in nanosheets stacked several layers thick. In the gel phase, the nanosheets are crystalline and form honeycomb lattices. The use of the Zincke reaction has previously been limited to the synthesis of small viologen molecules and conjugated viologen oligomers. Its application here expands the repertoire of tools for the fabrication of covalent organic networks (which are usually prepared by dynamic covalent chemistry) and for the synthesis of viologen-based materials. All three materials - HT, HS, and COGF - serve as efficient adsorbents of iodine due to the presence of the cationic viologen linker and, in the cases of HT and HS, permanent porosity.

    Original languageEnglish (US)
    Pages (from-to)9558-9565
    Number of pages8
    JournalJournal of the American Chemical Society
    Volume139
    Issue number28
    DOIs
    StatePublished - Jul 19 2017

    Fingerprint

    Viologens
    Nanosheets
    Gels
    Microwaves
    Ostwald ripening
    Iodine
    Oligomers
    Crystal lattices
    Adsorbents
    Porosity
    Heating
    Crystalline materials
    Fabrication
    Molecules

    ASJC Scopus subject areas

    • Catalysis
    • Chemistry(all)
    • Biochemistry
    • Colloid and Surface Chemistry

    Cite this

    Das, G., Skorjanc, T., Sharma, S. K., Gándara, F., Lusi, M., Shankar Rao, D. S., ... Trabolsi, A. (2017). Viologen-Based Conjugated Covalent Organic Networks via Zincke Reaction. Journal of the American Chemical Society, 139(28), 9558-9565. https://doi.org/10.1021/jacs.7b02836

    Viologen-Based Conjugated Covalent Organic Networks via Zincke Reaction. / Das, Gobinda; Skorjanc, Tina; Sharma, Sudhir Kumar; Gándara, Felipe; Lusi, Matteo; Shankar Rao, D. S.; Vimala, Sridurai; Krishna Prasad, Subbarao; Raya, Jesus; Han, Dong Suk; Jagannathan, Ramesh; Olsen, John Carl; Trabolsi, Ali.

    In: Journal of the American Chemical Society, Vol. 139, No. 28, 19.07.2017, p. 9558-9565.

    Research output: Contribution to journalArticle

    Das, G, Skorjanc, T, Sharma, SK, Gándara, F, Lusi, M, Shankar Rao, DS, Vimala, S, Krishna Prasad, S, Raya, J, Han, DS, Jagannathan, R, Olsen, JC & Trabolsi, A 2017, 'Viologen-Based Conjugated Covalent Organic Networks via Zincke Reaction', Journal of the American Chemical Society, vol. 139, no. 28, pp. 9558-9565. https://doi.org/10.1021/jacs.7b02836
    Das G, Skorjanc T, Sharma SK, Gándara F, Lusi M, Shankar Rao DS et al. Viologen-Based Conjugated Covalent Organic Networks via Zincke Reaction. Journal of the American Chemical Society. 2017 Jul 19;139(28):9558-9565. https://doi.org/10.1021/jacs.7b02836
    Das, Gobinda ; Skorjanc, Tina ; Sharma, Sudhir Kumar ; Gándara, Felipe ; Lusi, Matteo ; Shankar Rao, D. S. ; Vimala, Sridurai ; Krishna Prasad, Subbarao ; Raya, Jesus ; Han, Dong Suk ; Jagannathan, Ramesh ; Olsen, John Carl ; Trabolsi, Ali. / Viologen-Based Conjugated Covalent Organic Networks via Zincke Reaction. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 28. pp. 9558-9565.
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