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Lookup NU author(s): Dr Miguel Galindo-Cuesta, Jennifer Hannant, Dr Ross Harrington, Professor William Clegg, Dr Ben Horrocks, Dr Andrew Pike, Professor Andrew HoultonORCiD
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A series of modified nucleosides based on thymidine have been prepared by Pd-catalysed cross-coupling between N-alkyl-alkynyl functionalised pyrrolyl- (py), 2-(2-thienyl)pyrrolyl- (tp) or 2,5-bis(2-thienyl) pyrrolyl (tpt) groups with 5-iodo-2'-deoxyuridine. The length of the alkyl chain linking the nucleoside and pyrrolyl-containing unit, N(CH2)(n) C C-nucleoside (where n = 1-3) was also varied. The compounds have been characterised by H-1 NMR, ES-MS, UV-vis, cyclic voltammetry (CV) and, in some cases, single-crystal X-ray diffraction. Cyclic voltammetry studies demonstrated that all the py-, tp- and tpt-alkynyl derivatives 1-7 can be electrochemically polymerised to form conductive materials. It was found that increasing the N-alkyl chain length in these cases resulted in only minor changes in the oxidation potential. The same behaviour was observed for the tp- and tpt-modified nucleosides 9-12; however, the py-derivative, 8, produced a poorly conducting material. DFT calculations on the one-electron oxidised cation of the modified nucleosides bearing tp or tpt showed that spin density is located on the pyrrolyl and thienyl units in all cases and that the coplanarity of adjacent rings increases upon oxidation. In contrast, in the corresponding pyrrolyl cases the spin density is distributed over the whole molecule, suggesting that polymerisation does not occur solely at the pyrrolyl-Ca position and the conjugation is interrupted.
Author(s): Galindo MA, Hannant J, Harrington RW, Clegg W, Horrocks BR, Pike AR, Houlton A
Publication type: Article
Publication status: Published
Journal: Organic & Biomolecular Chemistry
Year: 2011
Volume: 9
Issue: 5
Pages: 1555-1564
Print publication date: 01/01/2011
ISSN (print): 1477-0520
ISSN (electronic): 1477-0539
Publisher: Royal Society of Chemistry
URL: http://dx.doi.org/10.1039/c0ob00466a
DOI: 10.1039/c0ob00466a
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