Details

Autor(en) / Beteiligte

• Slater, Anna G
• Hu, Ya
• Yang, Lixu
• Argent, Stephen P
• Lewis, William
• Blunt, Matthew O
• Champness, Neil R

Titel

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

Ist Teil von

• Chemical science (Cambridge), 2015-01, Vol.6 (2), p.1562-1569

Ort / Verlag

England

Erscheinungsjahr

2015

Link zum Volltext

Quelle

Electronic Journals Library

Beschreibungen/Notizen

• 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- -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 ( = 6.1 ± 3.0 M ) is relatively weak in comparison to the heteromolecular interaction between mono-TP and 9-propyladenine ( = 91.8 ± 20.5 M ). 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.