Self‐Assembled Monolayers of Thiolates on Metals as a Form of Nanotechnology

Love, J. Christopher; Estroff, Lara A.; Kriebel, Jennah K.; Nuzzo, Ralph G.; Whitesides, George M.

doi:10.1002/chin.200532281

Cited by 1,277 publications

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“…These strong Hbonds drive the TegA chains together and lead to segregation in the mixed MDA-TegA SAM. are ligand-exchanged first with the TegA thiol, and then with the MUA thiol, in order to reach a total coverage ratio of 5 thiol·nm -2 , close to the value employed for calculations and commonly used to reach full coverage [40][41] . To assess phase segregation in the organic corona, we use transmission electron microscopy (TEM) in combination with a strategy to enhance contrast.…”

Section: Since Our Partially (Figures 3a-d) and Fully (Figures 3e-h) mentioning

confidence: 97%

Nanophase Segregation of Self-Assembled Monolayers on Gold Nanoparticles

et al. 2017

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Nanophase segregation of a bi-component thiol self-assembled monolayer is predicted using atomistic molecular dynamics simulations and experimentally confirmed. The simulations suggest the formation of domains rich in acid-terminated chains, on one hand, and of domains rich in amide-functionalized ethylene glycol oligomers, on the other hand. In particular, within the amide-ethylene glycol oligomers region, a key role is played by the formation of inter-chain hydrogen bonds. The predicted phase segregation is experimentally confirmed by the synthesis of 35 and 15 nm gold nanoparticles functionalized with several binary mixtures of ligands. An extensive study by transmission electron microscopy and electron tomography using silica selective heterogeneous nucleation on acid-rich domains to provide electron contrast supports simulations and highlights patchy nanoparticles with a trend towards Janus nano-objects depending on the nature of the ligands and the particle size. These results validate our computational platform as an effective tool to predict nanophase separation in organic mixtures on a surface and drive further exploration of advanced nanoparticle functionalization.

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Section: Since Our Partially (Figures 3a-d) and Fully (Figures 3e-h) mentioning

confidence: 97%

Nanophase Segregation of Self-Assembled Monolayers on Gold Nanoparticles

et al. 2017

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“…[1][2][3][4][5] SAM functionalization provides a powerful, yet simple way to manipulate the chemical, electrical and optical properties of surfaces, with the ability to tune the material's macroscopic properties. 6 This is the case for dye-sensitized solar cells (DSCs) where a SAM of dye molecules sensitizes a semiconductor in order to harvest light. DSCs provide a viable alternative to traditional semiconductor solar cells due to their high efficiency and low environmental and industrial 3 costs.…”

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confidence: 99%

In Situ Mapping of the Molecular Arrangement of Amphiphilic Dye Molecules at the TiO₂ Surface of Dye-Sensitized Solar Cells

Voïtchovsky

Astani

Tavernelli

et al. 2015

ACS Appl. Mater. Interfaces

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Citation for published item:o¤ %t hovskyD uF nd esh ri est niD xF nd vernelliD sF nd etre ultD xF nd othlis ergerD F nd tell iD pF nd qr¤ tzelD wF nd erne r rmsD rF @PHISA 9snEsitu m pping of the mole ul r rr ngement of mphiphili dye mole ules t the iyP surf e of dye sensitized sol r ellsF9D eg pplied m teri ls interf esFD U @PHAF ppF IHVQREIHVRPF Further information on publisher's website: httpXGGdxFdoiForgGIHFIHPIG s miFS HITQV Publisher's copyright statement: This document is the Accepted Manuscript version of a Published Work that appeared in nal form in ACS applied materials interfaces, copyright c 2015 American Chemical Society after peer review and technical editing by the publisher. To access the nal edited and published work see http://dx.doi.org/10.1021/acsami.5b01638. Additional information:Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. Just Accepted "Just Accepted" manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides "Just Accepted" as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. "Just Accepted" manuscripts appear in full in PDF format accompanied by an HTML abstract. "Just Accepted" manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). "Just Accepted" is an optional service offered to authors. Therefore, the "Just Accepted" Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the "Just Accepted" Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these "Just Accepted" manuscripts. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59

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“…1 Important examples include ligation of gold nanoparticles, 2, 3 two probe conductance measurements of single molecules, [4][5][6][7] and surface functionalization of Au(111) by Self-Assembled Monolayers (SAMs). 8,9 All of these applications rely on anchoring via strong Au-thiolate bonds. Even though thiolate SAMs are widespread, structural details of the anchor bond were discussed controversially for a long time.…”

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From Au–Thiolate Chains to Thioether Sierpiński Triangles: The Versatile Surface Chemistry of 1,3,5-Tris(4-mercaptophenyl)benzene on Au(111)

et al. 2016

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Self-assembly of 1,3,5-tris(4-mercaptophenyl)benzene (TMB) -a three-fold symmetric, thiol functionalized aromatic molecule -was studied on Au(111) with the aim to realize extended Authiolate linked molecular architectures. The focus lay on resolving thermally activated structural and chemical changes by a combination of microscopy and spectroscopy. Thereby Scanning Tunneling Microscopy provided submolecularly resolved structural information, while the chemical state of sulfur was assessed by X-ray Photoelectron Spectroscopy. Directly after room temperature deposition only less well ordered structures were observed. Mild annealing promoted the first structural transition into ordered molecular chains, partly organized in homochiral molecular braids. Further annealing led to self-similar Sierpi ski triangles, while annealing at even higher temperatures again resulted in mostly disordered structures. Both the irregular aggregates observed at room temperature and the chains were identified as metalorganic assemblies, whereby two out of the three intermolecular binding motifs are energetically equivalent according to Density Functional Theory simulations. The emergence of Sierpi ski triangles is driven by a chemical transformation, i.e. the conversion of coordinative Au-thiolate to covalent thioether linkages, and can be further understood by Monte Carlo simulations. The great structural variance of TMB on Au(111) can on one hand be explained by the energetic equivalence of two binding motifs. On the other hand, the unexpected chemical transition even enhances the structural variance and results in thiol-derived covalent molecular architectures.3 KEYWORDS surface chemistry, on-surface synthesis, thiolate, thioether, fractals, STM, XPS, DFT, Monte CarloThe notorious affinity of thiols to gold is beneficial for molecular nano-science. 1 Important examples include ligation of gold nanoparticles, 2, 3 two probe conductance measurements of single molecules, [4][5][6][7] and surface functionalization of Au(111) by Self-Assembled Monolayers (SAMs). 8,9 All of these applications rely on anchoring via strong Au-thiolate bonds. Even though thiolate SAMs are widespread, structural details of the anchor bond were discussed controversially for a long time. Yet, a consensus seems to be reached insofar as Au-thiolate complexes formed with gold adatoms play an important role. 10 The promising properties of RSAu-SR linkages, in particular their electric conductance and their ability to form spontaneously on Au(111) motivated the present study with the aim to utilize these linkages for extended molecular nanostructures. To this end 1,3,5-tris(4-mercaptophenyl)benzene (TMB) as a threefold functionalized and suitable model compound for network formation is studied on Au(111).Owing to both the extended triphenylbenzene backbone and the three-point anchoring via thiolate-surface bonds, planar adsorption is anticipated as an important prerequisite for extended networks. In contrast to SAMs, where the prevalent monothiols adopt upri...

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Self‐Assembled Monolayers of Thiolates on Metals as a Form of Nanotechnology

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 1,277 publications

References 1 publication

Nanophase Segregation of Self-Assembled Monolayers on Gold Nanoparticles

Nanophase Segregation of Self-Assembled Monolayers on Gold Nanoparticles

In Situ Mapping of the Molecular Arrangement of Amphiphilic Dye Molecules at the TiO₂ Surface of Dye-Sensitized Solar Cells

From Au–Thiolate Chains to Thioether Sierpiński Triangles: The Versatile Surface Chemistry of 1,3,5-Tris(4-mercaptophenyl)benzene on Au(111)

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Self‐Assembled Monolayers of Thiolates on Metals as a Form of Nanotechnology

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 1,277 publications

References 1 publication

Nanophase Segregation of Self-Assembled Monolayers on Gold Nanoparticles

Nanophase Segregation of Self-Assembled Monolayers on Gold Nanoparticles

In Situ Mapping of the Molecular Arrangement of Amphiphilic Dye Molecules at the TiO2 Surface of Dye-Sensitized Solar Cells

From Au–Thiolate Chains to Thioether Sierpiński Triangles: The Versatile Surface Chemistry of 1,3,5-Tris(4-mercaptophenyl)benzene on Au(111)

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In Situ Mapping of the Molecular Arrangement of Amphiphilic Dye Molecules at the TiO₂ Surface of Dye-Sensitized Solar Cells