Crystal-to-crystal photo-reversible polymerization mechanism of bis-thymine derivative

Akihiro Udagawa, Priscilla Johnston, Aya Sakon, Ryosuke Toyoshima, Hidehiro Uekusa, Hideko Koshima, Kei Saito, Toru Asahi

    Research output: Contribution to journalArticle

    Abstract

    Solid-state photo-polymerization in crystals can produce stereoregular polymer molecules in environmentally friendly solvent-free systems. The polymerization mechanism of bis-thymine derivatives, such as dimethyl-3,3′-(3,3′-(butane-1,4-diyl)bis(5-methyl-2,4-dioxo-3,4-dihydropyrimidine-3,1(2H)-diyl))dipropanoate (1), known as unique molecules that can topochemically and reversibly polymerize in the crystalline state via [2 + 2]-cycloaddition reactions upon UV irradiation, remained to be solved. In this manuscript, the crystal structure of the polymeric photoproduct (1P) from a bis-thymine derivative 1 was determined using ab initio powder X-ray diffraction data and applied to investigate the polymerization mechanism of bis-thymine derivatives. The topochemical polymerization was found to be achieved via [2 + 2]-cycloaddition with the flexible butyl chain between thyminyl rings relieving the distortion of whole structure derived from cyclobutane formation. The crystal structure of 1P also showed that it polymerized stereoregularly with trans-anti cyclobutane conformations.

    Original languageEnglish
    Pages (from-to)107317-107322
    Number of pages6
    JournalRSC Advances
    Volume6
    Issue number109
    DOIs
    Publication statusPublished - 2016

    Fingerprint

    Thymine
    Cyclobutanes
    Cycloaddition
    Polymerization
    Derivatives
    Crystals
    Crystal structure
    Molecules
    Photopolymerization
    Butane
    X ray powder diffraction
    Conformations
    Polymers
    Irradiation
    Crystalline materials

    ASJC Scopus subject areas

    • Chemistry(all)
    • Chemical Engineering(all)

    Cite this

    Udagawa, A., Johnston, P., Sakon, A., Toyoshima, R., Uekusa, H., Koshima, H., ... Asahi, T. (2016). Crystal-to-crystal photo-reversible polymerization mechanism of bis-thymine derivative. RSC Advances, 6(109), 107317-107322. https://doi.org/10.1039/c6ra24229d

    Crystal-to-crystal photo-reversible polymerization mechanism of bis-thymine derivative. / Udagawa, Akihiro; Johnston, Priscilla; Sakon, Aya; Toyoshima, Ryosuke; Uekusa, Hidehiro; Koshima, Hideko; Saito, Kei; Asahi, Toru.

    In: RSC Advances, Vol. 6, No. 109, 2016, p. 107317-107322.

    Research output: Contribution to journalArticle

    Udagawa, A, Johnston, P, Sakon, A, Toyoshima, R, Uekusa, H, Koshima, H, Saito, K & Asahi, T 2016, 'Crystal-to-crystal photo-reversible polymerization mechanism of bis-thymine derivative', RSC Advances, vol. 6, no. 109, pp. 107317-107322. https://doi.org/10.1039/c6ra24229d
    Udagawa A, Johnston P, Sakon A, Toyoshima R, Uekusa H, Koshima H et al. Crystal-to-crystal photo-reversible polymerization mechanism of bis-thymine derivative. RSC Advances. 2016;6(109):107317-107322. https://doi.org/10.1039/c6ra24229d
    Udagawa, Akihiro ; Johnston, Priscilla ; Sakon, Aya ; Toyoshima, Ryosuke ; Uekusa, Hidehiro ; Koshima, Hideko ; Saito, Kei ; Asahi, Toru. / Crystal-to-crystal photo-reversible polymerization mechanism of bis-thymine derivative. In: RSC Advances. 2016 ; Vol. 6, No. 109. pp. 107317-107322.
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