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Issue 109, 2016, Issue in Progress
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Crystal-to-crystal photo-reversible polymerization mechanism of bis-thymine derivative

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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 transanti cyclobutane conformations.

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

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Supplementary files

Article information


Submitted
29 Sep 2016
Accepted
02 Nov 2016
First published
02 Nov 2016

RSC Adv., 2016,6, 107317-107322
Article type
Paper

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

A. Udagawa, P. Johnston, A. Sakon, R. Toyoshima, H. Uekusa, H. Koshima, K. Saito and T. Asahi, RSC Adv., 2016, 6, 107317
DOI: 10.1039/C6RA24229D

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