Controlling the conformational changes in donor-acceptor [4]dendralenes through intramolecular charge-transfer processes

Alexander L. Kanibolotsky, John C. Forgie, Greg J. McEntee, M. Munsif A Talpur, Peter J. Skabara, Thomas D J Westeate, Joseph J W McDouall, Michael Auinge, Simon J. Coles, Michael B. Hursthouse

    Research output: Contribution to journalArticlepeer-review

    Abstract

    The synthesis of two [4]-dendralene compounds incorporating thiophene-(p-nitrophenyl) donor-acceptor units is presented. The dendralenes adopt two different conformers in solution and solid state and the transformation between the structures can be controlled by light and heat. The electrondonating components of the dendralenes are represented by bromothienyl (in 13) and ethylenedioxythiophene(EDOT)-thienyl (in 15) end-groups. The most facile transformation involves the isomerisation of donor-acceptor conjugated systems (a conformers) into structures in which only the thiophenes are conjugated (b conformers), and this process is driven by ambient light. The structures of the two conformers of compound 13 are confirmed by singlecrystal X-ray diffraction studies and the structural changes in both compounds have been monitored by 1H NMR spectroscopy and absorption studies. The transformations were found to be first-order processes with rate constants of k = 0.0027 s -1 and k = 0.00022 s-1 for 13 and 15, respectively. Density functional theory calculations at the B3LYP/6-31G* level give credence to the proposed mechanism for the a→b conversion, which involves photoinduced intramolecular charge transfer (ICT) as the key step. The EDOT derivative (15) can be polymerised by electrochemical oxidation and a combination of cyclic voltammetry and UV/Vis spectroelectrochemical experiments indicate that the a conformer can be trapped and stabilised in the solid state. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.
    Original languageEnglish
    Pages (from-to)11581-11593
    Number of pages12
    JournalChemistry - A European Journal
    Volume15
    Issue number43
    DOIs
    Publication statusPublished - 2 Nov 2009

    Keywords

    • Conformational isomerization
    • Crystallography
    • Dendralenes
    • Electrochemistry
    • Molecular modeling

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