Organothiols Self-Assembled onto Gold: Evidence for Deprotonation of the Sulfur-Bound Hydrogen and Charge Transfer from Thiolate

Ansar, Siyam M.; Perera, Ganganath S.; Jiang, Dongping; Holler, Robert A.; Zhang, Dongmao

doi:10.1021/jp312836q

Cited by 45 publications

(82 citation statements)

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“…[2][3][4][5][6] Understanding the binding properties and structure of the Au-thiolate motifs, and the properties of the Au-S interface in general, is of importance for different research areas such as nanoelectronics and catalysis. 7,8 It has been demonstrated for example that the Au-S interface is quite flexible.…”

Section: Introductionmentioning

confidence: 99%

Structural Information on the Au–S Interface of Thiolate-Protected Gold Clusters: A Raman Spectroscopy Study

et al. 2014

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The Raman spectra of a series of monolayer-protected gold clusters were investigated with special emphasis on the Au-S modes below 400 cm(-1). These clusters contain monomeric (SR-Au-SR) and dimeric (SR-Au-SR-Au-SR) gold-thiolate staples in their surface. In particular, the Raman spectra of Au-25(2-PET)(18)](0/-), Au-38(2-PET)(24), Au-40(2-PET)(24), and Au-144(2-PET)(60) (2-PET = 2-phenylethylthiol) were measured in order to study the influence of the cluster size and therefore the composition with respect to the monomeric and dimeric staples. Additionally, spectra of Au-25(2-PET)(18-2x) (S-/rac-BINAS)(x) (BINAS = 1,1'-binaphthy1-2,2'-dithiol), Au-25(CamS)(18) (CamS = 1R,4S-camphorthiol), and Au(n)BINAS(m) were measured to identify the influence of the thiolate ligand on the Au-S vibrations. The vibrational spectrum of Au-38(SCH3)(24) was calculated which allows the assignment of bands to vibrational modes of the different staple motifs. The spectra are sensitive to the size of the cluster and the nature of the ligand. Au-S-C bending around 200 cm(-1) shifts to slightly higher wavenumbers for the dimeric as compared to the monomeric staples. Radial Au-S modes (250-325 cm(-1)) seem to be sensitive toward the staple composition and the bulkiness of the ligand, having higher intensities for long staples and shifting to higher wavenumbers for sterically more demanding ligands. The introduction of only one BINAS dithiol has a dramatic influence on the Au-S vibrations because the molecule bridges two staples which changes their vibrational properties completely. 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 ...

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Section: Introductionmentioning

confidence: 99%

Structural Information on the Au–S Interface of Thiolate-Protected Gold Clusters: A Raman Spectroscopy Study

et al. 2014

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“…24−27 Mechanistic study revealed that the organothiol binding to AuNPs occurs by releasing the The Journal of Physical Chemistry C Article sulfur-bound hydrogen atoms as protons, thereby the organothiol is in thiolate form on AuNPs. 24 In contrast, organothiol interacting with AgNPs proceeds by converting the surface silver oxide and surface silver atom into silver thiolate salt. 25,26 The presence of a relatively thick layer of the silver thiolate salt on AgNPs (Figures 6 and S9 in the Supporting Information) exclude the possibility for the dithiols to cross-link two AgNP as monolayer dithiolate linker.…”

Section: ■ Introductionmentioning

confidence: 99%

Can Para-Aryl-Dithiols Cross-Link Two Plasmonic Noble Nanoparticles as Monolayer Dithiolate Spacers?

et al. 2015

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Para-aryl-dithiols (PADTs, HS-(C 6 H 4 ) n -SH, n = 1, 2, and 3) have been used extensively in molecular electronics, surface-enhanced Raman spectroscopy (SERS), and quantum electron tunneling between two gold or silver nanoparticles (AuNPs and AgNPs). One popular belief is that these dithiols cross-link noble metal nanoparticles (NPs) as monolayer dithiolate spacers. Reported herein is our finding that PADTs predominantly exist as monothiolate forms on AuNPs or AgNPs. No PADT-induced NP cross-linking was observed regardless of the NP/PADT concentration ratios. Moreover, only one PADT thiol can be deprotonated even when PADTs are treated with concentrated NaOH or AgNO 3 solutions. In contrast, 1,4-benzenedimethanethiol (HS-CH 2 -(C 6 H 4 ) 1 -CH 2 -SH) and alkyl dithiol 1,2-ethanedithiol can be dithiolated on AuNPs and AgNPs, and in excess NaOH and AgNO 3 solutions. This study should be of broad importance for plasmonic NP research given the popularity of PADTs in molecular electronics and SERS applications.

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“…This can be especially true for organodithiol interactions with AuNPs and AgNPs. Unlike monothiols that bind to AuNPs as monothiolates by releasing its sulfur-bound hydrogen as proton, 27 organodithiol binding to NPs is much more complicated. It can bind as a monomer on the same NP in both monothiolate and dithiolate forms (Figure 1(A)), or as a dithiolate monomer bridging two AuNPs (Figure 1(B)).…”

Section: Introductionmentioning

confidence: 99%

“…27,[33][34][35][36] The goal of this current study is to determine the structure and compositions of the alkanedithiol (ADT, HS-(CH 2 ) n -SH) adsorbed onto AuNPs and AgNPs in water, using a combination of SERS, inductively-coupled were purchased within the past four months and they are used as received. The reagent purity are all 95% or above.…”

Section: Introductionmentioning

confidence: 99%

Structures and Conformations of Alkanedithiols on Gold and Silver Nanoparticles in Water

et al. 2015

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Organodithiols with two distal thiols have been used extensively in gold and silver nanoparticle (AuNP and AgNP) applications. However, understanding the structures and conformations of organodithiols on these nanoparticles is challenging. Reported in this work is a combined surface enhanced Raman spectroscopy (SERS), transmission electron microscope (TEM), inductively-coupled plasma mass-spectrometry (ICP-MS), and localized surface plasmonic resonance (LSPR) study of alkyldithiol (ADT, (HS-(CH 2 ) n -SH, n= 2, 4, and 6) interactions with AuNPs and AgNPs in water. These complementary techniques revealed a series of new insights that would not be possible using individual methods. A large-fraction of ADTs lies flat on AuNP surfaces. The upright ADTs are dimerized horizontally through disulfide-bond, or remain as monothiolates on the AuNP surfaces. Possibility of significant amount of vertically disulfide-linked organodithiol on the surface is excluded on the basis of ICP-MS and AuNP LSPR experiments. ADTs induced significant AgNP disintegrations in which ADTs are predominantly in dithiolate forms. This work highlights the extraordinary complexity of organodithiol interactions with plasmonic nanoparticles. The insights provided in this work will be important for enhancing fundamental understanding of the structure and properties of organothiol-functionalized AgNPs and AuNPs.

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Organothiols Self-Assembled onto Gold: Evidence for Deprotonation of the Sulfur-Bound Hydrogen and Charge Transfer from Thiolate

Cited by 45 publications

References 39 publications

Structural Information on the Au–S Interface of Thiolate-Protected Gold Clusters: A Raman Spectroscopy Study

Structural Information on the Au–S Interface of Thiolate-Protected Gold Clusters: A Raman Spectroscopy Study

Can Para-Aryl-Dithiols Cross-Link Two Plasmonic Noble Nanoparticles as Monolayer Dithiolate Spacers?

Structures and Conformations of Alkanedithiols on Gold and Silver Nanoparticles in Water

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