Journal
SURFACE SCIENCE
Volume 643, Issue -, Pages 91-97Publisher
ELSEVIER
DOI: 10.1016/j.susc.2015.08.013
Keywords
Metal-directed assembly; Surface coordination chemistry; Metal-organic coordination polymers; Molecular wires
Categories
Funding
- European Union via ERC [247299]
- Polish Ministry of Science and Higher Education [DI2011 011941]
- Munich-Centre for Advanced Photonics [MAP C 1.4]
- TUM Institute of Advanced Study (IAS)
- [RYC-2012-11133]
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Understanding the dynamics and thermal stability of metallosupramolecular chains on surfaces is of relevance for the development of molecular connectors in nanoelectronics or other fields. Here we present a combined study using temperature-controlled STM and Monte Carlo simulations to explore the behavior of metal-organic porphyrin chains on Cu(111) based on two-fold pyridyl-Cu-pyridyl coordination motifs. We monitor their behavior in the 180-360 K range, revealing three thermal regimes: i) flexibility up to 240 K, ii) diffusion of chain fragments and partial dissociation into a fluid phase for T > 240 K, and iii) full dissolution with temperatures exceeding similar to 320 K. The experimentally estimated reaction enthalpy of the metal-organic bonding is similar to 0.6 eV. Monte Carlo simulations reproduce qualitatively our STM observations and reveal the preference for linear and extended supramolecular chains with reduced substrate temperatures. (C) 2015 Elsevier B.V. All rights reserved.
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