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Sequential nested assembly at the liquid/solid interface

Research output: Contribution to journalArticle



Baharan Karamzadeh, Thomas Eaton, David Muñoz Torres, Izabela Cebula, Marcel Mayor, Manfred Buck

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Studying the stepwise assembly of a four component hybrid structure on Au(111)/mica, the pores of a hydrogen bonded bimolecular network of 3,4:9,10-perylenetetracarboxylic diimide (PTCDI) and 1,3,5-triazine-2,4,6-triamine (melamine) were partitioned by three and four-armed molecules based on oligo([biphenyl]-4-ylethynyl)benzene, followed by the templated adsorption of either C60 fullerene or adamantane thiol molecules. The characterisation by ambient scanning tunneling microscopy (STM) reveals that the pore modifiers exhibit a dynamics which pronouncedly depends on the molecular structure. The three-armed molecule 1,3,5-tris([1,1'-biphenyl]-4-ylethynyl)benzene (3BPEB) switches between two symmetry equivalent configurations on a time scale fast compared to the temporal resolution of the STM. Derivatisation of 3BPEB by hydroxyl groups substantially reduces the switching rate. For the four-armed molecule configurational changes are observed only occasionally. The observation of isolated fullerenes and small clusters of adamantane thiol molecules, which are arranged in a characteristic fashion, reveals the templating effect of the trimolecular supramolecular network. However, the fraction of compartments filled by guest molecules is significantly below one for both the thermodynamically controlled adsorption of C60 and the kinetically controlled adsorption of the thiol with the latter causing a partial removal of the pore modifier. On the one hand, demonstrating the feasibility of templating by nested assembly, the experiments, on the other hand, pinpoint the requirement for the energy landscape to be tolerant to variations in the assembly process.


Original languageEnglish
JournalFaraday Discussions
VolumeAdvance online
Early online date26 Apr 2017
StateE-pub ahead of print - 26 Apr 2017

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