Solvent-Dependent Stabilization of Metastable Monolayer Polymorphs at the Liquid–Solid Interface

Self-assembly of 1,3,5-tris(4′-biphenyl-4″-carbonitrile)benzene monolayers was studied at the liquid–solid interface by scanning tunneling microscopy. Application of different fatty acid homologues as solvents revealed a solvent-induced polymorphism. Yet, tempering triggered irreversible phase trans...

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Bibliographic Details
Published in:ACS nano 2013-08, Vol.7 (8), p.6711-6718
Main Authors: Sirtl, Thomas, Song, Wentao, Eder, Georg, Neogi, Subhadip, Schmittel, Michael, Heckl, Wolfgang M, Lackinger, Markus
Format: Article
Language:English
Subjects:
Adsorption
Computer Simulation
Fatty Acids - chemistry
Gases
Graphite - chemistry
Heat treatment
Kinetics
Liquid-solid interfaces
Metastability
Microscopy, Scanning Tunneling
Monolayers
Nanostructure
Phase transformations
Pressure
Self assembly
Solvents
Solvents - chemistry
Surface Properties
Temperature
Thermodynamics
Ultrahigh vacuum
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Summary:Self-assembly of 1,3,5-tris(4′-biphenyl-4″-carbonitrile)benzene monolayers was studied at the liquid–solid interface by scanning tunneling microscopy. Application of different fatty acid homologues as solvents revealed a solvent-induced polymorphism. Yet, tempering triggered irreversible phase transitions of the initially self-assembled monolayers, thereby indicating their metastability. Interestingly, in either case, the same thermodynamically more stable and more densely packed monolayer polymorph was obtained after thermal treatment, irrespective of the initial structure. Again, the same densely packed structure was obtained in complementary solvent-free experiments conducted under ultrahigh vacuum conditions. Thus, self-assembly of metastable polymorphs at room temperature is explained by adsorption of partially solvated species under kinetic control. The irreversible phase transitions are induced by thermal desolvation, that is, desorption of coadsorbed solvent molecules.
ISSN:1936-0851
1936-086X
DOI:10.1021/nn4014577