Odd-even effects in aryl-substituted alkanethiolate SAMs: nonsymmetrical attachment of aryl unit and its impact on the SAM structure

Due to non-symmetric attachment of the anthracene unit to the alkanethiolate linker, the respective monolayers on Au(111) exhibit low extent of the odd-even effects and distinct polymorphism, showing, at the same time, high structural order. - , - - Aryl-substit...

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Main Authors: Azzam, Waleed (Author) , Subaihi, Abdu (Author) , Rohwerder, Michael (Author) , Bashir, Asif (Author) , Terfort, Andreas (Author) , Zharnikov, Michael (Author)
Format: Article (Journal)
Language:English
Published: 12 Feb 2024
In: Physical chemistry, chemical physics
Year: 2024, Volume: 26, Issue: 9, Pages: 7563-7572
ISSN:1463-9084
DOI:10.1039/D4CP00311J
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1039/D4CP00311J
Verlag, lizenzpflichtig, Volltext: https://xlink.rsc.org/?DOI=D4CP00311J
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Author Notes:Waleed Azzam, Abdu Subaihi, Michael Rohwerder, Asif Bashir, Andreas Terfort and Michael Zharnikov
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Summary:Due to non-symmetric attachment of the anthracene unit to the alkanethiolate linker, the respective monolayers on Au(111) exhibit low extent of the odd-even effects and distinct polymorphism, showing, at the same time, high structural order. - , - - Aryl-substituted alkanethiolate (AT) self-assembled monolayers (SAMs) exhibit typically so-called odd-even effects, - viz. - systematic variations in the film structure, packing density, and molecular inclination depending on the parity of the number of the methylene units in the alkyl linker, - n - . As an exception to this rule, ATs carrying an anthracen-2-yl group (Ant- - n - ) as tail group were reported to have different behavior due the non-symmetric attachment of the anthracene unit to the AT linker, providing additional degree of freedom for the molecular organization and allowing for partial compensation of the odd-even effects. In this context, the structure of SAMs formed by adsorption of anthracene-substituted ATs (Ant- - n - ; - n - = 1-6) at room temperature on Au(111) substrate was investigated by high-resolution scanning tunnelling microscopy (STM). Most of these SAMs exhibit a coexistence of two different ordered phases, some of which are common for either - n - = odd or - n - = even while other vary over the series, showing a broad variety of different structures. The average packing density of the Ant- - n - SAMs, derived from the analysis of the STM data, varies by 7.5-10% depending on the parity of - n - , being, as expected, higher for - n - = odd. The respective extent of the odd-even effects is noticeably lower than that usually observed for other aryl-substituted monolayers (∼25%), which goes in line with the previous findings and emphasizes the impact of the non-symmetric attachment of the aromatic unit.
Item Description:Gesehen am 05.08.2024
Physical Description:Online Resource
ISSN:1463-9084
DOI:10.1039/D4CP00311J