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Issue 2, 2015
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Thymine functionalised porphyrins, synthesis and heteromolecular surface-based self-assembly

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Abstract

The synthesis and surface-based self-assembly of thymine-functionalised porphyrins is described. Reaction of 1-formylphenyl-3-benzoyl-thymine with suitable pyrollic species leads to the formation of tetra-(phenylthymine)porphyrin (tetra-TP) or mono-thymine-tri-(3,5-di-tert-butylphenyl)porphyrin (mono-TP). Single crystal X-ray diffraction studies demonstrate the self-association of mono-TP in the solid state through thymine⋯thymine hydrogen-bonding interactions but in solution this interaction (Kd = 6.1 ± 3.0 M−1) is relatively weak in comparison to the heteromolecular interaction between mono-TP and 9-propyladenine (K = 91.8 ± 20.5 M−1). STM studies of the tetratopic hydrogen-bonding tecton, tetra-TP, deposited on an HOPG substrate reveal the formation of an almost perfectly square self-assembled lattice through thymine⋯thymine hydrogen-bonding. Co-deposition of tetra-TP with 9-propyladenine leads to the adoption of preferable thymine⋯adenine interactions leading to the formation of a heteromolecular tetra-TP⋯9-propyladenine hydrogen bonded array including both Watson–Crick thymine⋯adenine interactions and adenine⋯adenine hydrogen-bonding. The studies demonstrate a pathway for the self-assembly of tetratopic hydrogen-bonding tectons and the use of preferential heteromolecular thymine⋯adenine interactions for the disruption of the homomolecular tetra-TP array. Studies of the self-assembly of tetra-TP and 9-propyladenine demonstrate a strong dependence on overall concentration and molar ratio of components indicating the importance of kinetic effects in surface self-assembly processes.

Graphical abstract: Thymine functionalised porphyrins, synthesis and heteromolecular surface-based self-assembly

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Publication details

The article was received on 14 Nov 2014, accepted on 11 Dec 2014 and first published on 11 Dec 2014


Article type: Edge Article
DOI: 10.1039/C4SC03531C
Citation: Chem. Sci., 2015,6, 1562-1569
  • Open access: Creative Commons BY license
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    Thymine functionalised porphyrins, synthesis and heteromolecular surface-based self-assembly

    A. G. Slater, Y. Hu, L. Yang, S. P. Argent, W. Lewis, M. O. Blunt and N. R. Champness, Chem. Sci., 2015, 6, 1562
    DOI: 10.1039/C4SC03531C

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