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Issue 2, 2015

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

Supplementary files

Article information


Submitted
14 Nov 2014
Accepted
11 Dec 2014
First published
11 Dec 2014

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2015,6, 1562-1569
Article type
Edge Article
Author version available

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

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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