Title |
Thermal selectivity of intermolecular versus intramolecular reactions on surfaces
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Published in |
Nature Communications, March 2016
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DOI | 10.1038/ncomms11002 |
Pubmed ID | |
Authors |
Borja Cirera, Nelson Giménez-Agulló, Jonas Björk, Francisco Martínez-Peña, Alberto Martin-Jimenez, Jonathan Rodriguez-Fernandez, Ana M. Pizarro, Roberto Otero, José M. Gallego, Pablo Ballester, José R. Galan-Mascaros, David Ecija |
Abstract |
On-surface synthesis is a promising strategy for engineering heteroatomic covalent nanoarchitectures with prospects in electronics, optoelectronics and photovoltaics. Here we report the thermal tunability of reaction pathways of a molecular precursor in order to select intramolecular versus intermolecular reactions, yielding monomeric or polymeric phthalocyanine derivatives, respectively. Deposition of tetra-aza-porphyrin species bearing ethyl termini on Au(111) held at room temperature results in a close-packed assembly. Upon annealing from room temperature to 275 °C, the molecular precursors undergo a series of covalent reactions via their ethyl termini, giving rise to phthalocyanine tapes. However, deposition of the tetra-aza-porphyrin derivatives on Au(111) held at 300 °C results in the formation and self-assembly of monomeric phthalocyanines. A systematic scanning tunnelling microscopy study of reaction intermediates, combined with density functional calculations, suggests a [2+2] cycloaddition as responsible for the initial linkage between molecular precursors, whereas the monomeric reaction is rationalized as an electrocyclic ring closure. |
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Demographic breakdown
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Members of the public | 1 | 100% |
Mendeley readers
Geographical breakdown
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Germany | 1 | 1% |
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Researcher | 10 | 15% |
Student > Master | 7 | 10% |
Professor > Associate Professor | 6 | 9% |
Student > Doctoral Student | 5 | 7% |
Other | 14 | 21% |
Unknown | 10 | 15% |
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Materials Science | 10 | 15% |
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Other | 3 | 4% |
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