Chain-Length Effects on Molecular Conformation in and Chirality of Self-Assembled Monolayers of Alkoxylated Benzo[c]cinnoline Derivatives on Highly Oriented Pyrolytic Graphite

Self-assembled monolayers (SAMs) of nitrile-substituted oligo(phenylene ethynylene) thiols (NC-OPEn) with a variable chain length n (n ranging from one to three structural units) on Au(111) were studied by synchrotron-based high-resolution X-ray photoelectron spectroscopy and near-edge absorption fine-structure spectroscopy. The experimental data suggest that the NC-OPEn molecules form well-defined SAMs on Au(111), with all the molecules bound to the substrate through the gold–thiolate anchor and the nitrile tail groups located at the SAM–ambient interface. The packing density in these SAMs was found to be close to that of alkanethiolate monolayers on Au(111), independent of the chain length. Similar behavior was found for the molecular inclination, with an average tilt angle of ~33–36° for all the target systems. In contrast, the average twist of the OPEn backbone (planar conformation) was found to depend on the molecular length, being close to 45° for the films comprising the short OPE chains and ~53.5° for the long chains. Analysis of the data suggests that the attachment of the nitrile moiety, which served as a spectroscopic marker group, to the OPEn backbone did not significantly affect the molecular orientation in the SAMs.

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Chain length effect of alkanethiol self-assembled monolayers on the maximum spreading ratio of impacting water droplets

Colloids and Surfaces A Physicochemical and Engineering Aspects ◽

10.1016/j.colsurfa.2005.03.015 ◽

2005 ◽

Vol 260 (1-3) ◽

pp. 255-263 ◽

Cited By ~ 7

Author(s):

Yu-Wen Chang ◽

Chijioke Ukiwe ◽

Daniel Y. Kwok

Keyword(s):

Chain Length ◽

Self Assembled Monolayers ◽

Water Droplets ◽

Length Effect ◽

Assembled Monolayers ◽

Self Assembled ◽

Maximum Spreading

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Surface vibrations in alkanethiol self-assembled monolayers of varying chain length

The Journal of Chemical Physics ◽

10.1063/1.1643353 ◽

2004 ◽

Vol 120 (8) ◽

pp. 3880-3886 ◽

Cited By ~ 19

Author(s):

A. W. Rosenbaum ◽

M. A. Freedman ◽

S. B. Darling ◽

I. Popova ◽

S. J. Sibener

Keyword(s):

Chain Length ◽

Self Assembled Monolayers ◽

Assembled Monolayers ◽

Surface Vibrations ◽

Self Assembled

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Chain-Length-Dependent Vibrational Resonances in Alkanethiol Self-Assembled Monolayers Observed on Plasmonic Nanoparticle Substrates

Nano Letters ◽

10.1021/nl062283k ◽

2006 ◽

Vol 6 (11) ◽

pp. 2617-2621 ◽

Cited By ~ 40

Author(s):

Carly S. Levin ◽

Benjamin G. Janesko ◽

Rizia Bardhan ◽

Gustavo E. Scuseria ◽

Jeffrey D. Hartgerink ◽

...

Keyword(s):

Chain Length ◽

Self Assembled Monolayers ◽

Plasmonic Nanoparticle ◽

Assembled Monolayers ◽

Self Assembled ◽

Vibrational Resonances

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Self-assembled monolayers of shape-persistent macrocycles on graphite: interior design and conformational polymorphism

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.10.294 ◽

2014 ◽

Vol 10 ◽

pp. 2774-2782 ◽

Cited By ~ 5

Author(s):

Joscha Vollmeyer ◽

Friederike Eberhagen ◽

Sigurd Höger ◽

Stefan-S Jester

Keyword(s):

Interior Design ◽

Pyrolytic Graphite ◽

Self Assembled Monolayers ◽

Scanning Tunneling ◽

Tunneling Microscopy ◽

Conformational Polymorphism ◽

Assembled Monolayers ◽

Self Assembled ◽

Solid Liquid Interface ◽

Solid Liquid

Three shape-persistent naphthylene–phenylene–acetylene macrocycles of identical backbone structures and extraannular substitution patterns but different (empty, apolar, polar) nanopore fillings are self-assembled at the solid/liquid interface of highly oriented pyrolytic graphite and 1,2,4-trichlorobenzene. Submolecularly resolved images of the resulting two-dimensional (2D) crystalline monolayer patterns are obtained by in situ scanning tunneling microscopy. A concentration-dependent conformational polymorphism is found, and open and more dense packing motifs are observed. For all three compounds alike lattice parameters are found, therefore the intermolecular macrocycle distances are mainly determined by their size and symmetry. This is an excellent example that the graphite acts as a template for the macrocycle organization independent from their specific interior.

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