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 journalArticleResearchpeer-review

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

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
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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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.",
author = "Akihiro Udagawa and Priscilla Johnston and Aya Sakon and Ryosuke Toyoshima and Hidehiro Uekusa and Hideko Koshima and Kei Saito and Toru Asahi",
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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

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 journalArticleResearchpeer-review

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AU - Sakon, Aya

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AU - Uekusa, Hidehiro

AU - Koshima, Hideko

AU - Saito, Kei

AU - Asahi, Toru

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