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Triptycene Tripods for the Formation of Highly Uniform and Densely Packed Self-Assembled Monolayers with Controlled Molecular Orientation

[Image: see text] When employing self-assembled monolayers (SAMs) for tuning surface and interface properties, organic molecules that enable strong binding to the substrate, large-area structural uniformity, precise alignment of functional groups, and control of their density are highly desirable. T...

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Autores principales: Ishiwari, Fumitaka, Nascimbeni, Giulia, Sauter, Eric, Tago, Hiromu, Shoji, Yoshiaki, Fujii, Shintaro, Kiguchi, Manabu, Tada, Tomofumi, Zharnikov, Michael, Zojer, Egbert, Fukushima, Takanori
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6483319/
https://www.ncbi.nlm.nih.gov/pubmed/30869881
http://dx.doi.org/10.1021/jacs.9b00950
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author Ishiwari, Fumitaka
Nascimbeni, Giulia
Sauter, Eric
Tago, Hiromu
Shoji, Yoshiaki
Fujii, Shintaro
Kiguchi, Manabu
Tada, Tomofumi
Zharnikov, Michael
Zojer, Egbert
Fukushima, Takanori
author_facet Ishiwari, Fumitaka
Nascimbeni, Giulia
Sauter, Eric
Tago, Hiromu
Shoji, Yoshiaki
Fujii, Shintaro
Kiguchi, Manabu
Tada, Tomofumi
Zharnikov, Michael
Zojer, Egbert
Fukushima, Takanori
author_sort Ishiwari, Fumitaka
collection PubMed
description [Image: see text] When employing self-assembled monolayers (SAMs) for tuning surface and interface properties, organic molecules that enable strong binding to the substrate, large-area structural uniformity, precise alignment of functional groups, and control of their density are highly desirable. To achieve these goals, tripod systems bearing multiple bonding sites have been developed as an alternative to conventional monodentate systems. Bonding of all three sites has, however, hardly been achieved, with the consequence that structural uniformity and orientational order in tripodal SAMs are usually quite poor. To overcome that problem, we designed 1,8,13-trimercaptomethyltriptycene (T1) and 1,8,13-trimercaptotriptycene (T2) as potential tripodal SAM precursors and investigated their adsorption behavior on Au(111) combining several advanced experimental techniques and state-of-the-art theoretical simulations. Both SAMs adopt dense, nested hexagonal structures but differ in their adsorption configurations and structural uniformity. While the T2-based SAM exhibits a low degree of order and noticeable deviation from the desired tripodal anchoring, all three anchoring groups of T1 are equally bonded to the surface as thiolates, resulting in an almost upright orientation of the benzene rings and large-area structural uniformity. These superior properties are attributed to the effect of conformationally flexible methylene linkers at the anchoring groups, absent in the case of T2. Both SAMs display interesting electronic properties, and, bearing in mind that the triptycene framework can be functionalized by tail groups in various positions and with high degree of alignment, especially T1 appears as an ideal docking platform for complex and highly functional molecular films.
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spelling pubmed-64833192019-04-26 Triptycene Tripods for the Formation of Highly Uniform and Densely Packed Self-Assembled Monolayers with Controlled Molecular Orientation Ishiwari, Fumitaka Nascimbeni, Giulia Sauter, Eric Tago, Hiromu Shoji, Yoshiaki Fujii, Shintaro Kiguchi, Manabu Tada, Tomofumi Zharnikov, Michael Zojer, Egbert Fukushima, Takanori J Am Chem Soc [Image: see text] When employing self-assembled monolayers (SAMs) for tuning surface and interface properties, organic molecules that enable strong binding to the substrate, large-area structural uniformity, precise alignment of functional groups, and control of their density are highly desirable. To achieve these goals, tripod systems bearing multiple bonding sites have been developed as an alternative to conventional monodentate systems. Bonding of all three sites has, however, hardly been achieved, with the consequence that structural uniformity and orientational order in tripodal SAMs are usually quite poor. To overcome that problem, we designed 1,8,13-trimercaptomethyltriptycene (T1) and 1,8,13-trimercaptotriptycene (T2) as potential tripodal SAM precursors and investigated their adsorption behavior on Au(111) combining several advanced experimental techniques and state-of-the-art theoretical simulations. Both SAMs adopt dense, nested hexagonal structures but differ in their adsorption configurations and structural uniformity. While the T2-based SAM exhibits a low degree of order and noticeable deviation from the desired tripodal anchoring, all three anchoring groups of T1 are equally bonded to the surface as thiolates, resulting in an almost upright orientation of the benzene rings and large-area structural uniformity. These superior properties are attributed to the effect of conformationally flexible methylene linkers at the anchoring groups, absent in the case of T2. Both SAMs display interesting electronic properties, and, bearing in mind that the triptycene framework can be functionalized by tail groups in various positions and with high degree of alignment, especially T1 appears as an ideal docking platform for complex and highly functional molecular films. American Chemical Society 2019-03-14 2019-04-10 /pmc/articles/PMC6483319/ /pubmed/30869881 http://dx.doi.org/10.1021/jacs.9b00950 Text en Copyright © 2019 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle Ishiwari, Fumitaka
Nascimbeni, Giulia
Sauter, Eric
Tago, Hiromu
Shoji, Yoshiaki
Fujii, Shintaro
Kiguchi, Manabu
Tada, Tomofumi
Zharnikov, Michael
Zojer, Egbert
Fukushima, Takanori
Triptycene Tripods for the Formation of Highly Uniform and Densely Packed Self-Assembled Monolayers with Controlled Molecular Orientation
title Triptycene Tripods for the Formation of Highly Uniform and Densely Packed Self-Assembled Monolayers with Controlled Molecular Orientation
title_full Triptycene Tripods for the Formation of Highly Uniform and Densely Packed Self-Assembled Monolayers with Controlled Molecular Orientation
title_fullStr Triptycene Tripods for the Formation of Highly Uniform and Densely Packed Self-Assembled Monolayers with Controlled Molecular Orientation
title_full_unstemmed Triptycene Tripods for the Formation of Highly Uniform and Densely Packed Self-Assembled Monolayers with Controlled Molecular Orientation
title_short Triptycene Tripods for the Formation of Highly Uniform and Densely Packed Self-Assembled Monolayers with Controlled Molecular Orientation
title_sort triptycene tripods for the formation of highly uniform and densely packed self-assembled monolayers with controlled molecular orientation
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6483319/
https://www.ncbi.nlm.nih.gov/pubmed/30869881
http://dx.doi.org/10.1021/jacs.9b00950
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