Functionalized Nanodiamonds Part 3:  Thiolation of Tertiary/Bridgehead Alcohols

Tkachenko, Boryslav A.; Fokina, Natalie A.; Chernish, Lesya V.; Dahl, Jeremy E. P.; Liu, Shenggao; Carlson, Robert M. K.; Fokin, Andrey A.; Schreiner, Peter R.

doi:10.1021/ol053136g

Cited by 76 publications

(68 citation statements)

References 34 publications

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“…Over the past two decades, SAMs of thiol-functionalized molecules on Au have emerged as one of the most convenient and widely used means for forming well-ordered films of small molecules 15 . With the recent success of site-specific functionalization of diamondoids [16][17][18][19][20] , it is now possible to use higher-diamondoids as molecular building blocks to yield materials with well-defined structures, including SAMs of higher-diamondoids. Self-assembled monolayers of adamantane-1-thiol, the smallest, most abundant, and most readily synthesized diamondoid, forms highly packed hexagonal layers on Au(111) reportedly with lower defect densities than alkane thiols, with a 7x7 reconstruction and 6.9 Å nearest neighbor distance [21][22][23] .…”

Section: Introductionmentioning

confidence: 99%

Near-Edge X-ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

et al. 2008

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Diamondoids, hydrocarbon molecules with cubic-diamond-cage structures, have unique properties with potential value for nanotechnology. The availability and ability to selectively functionalize this special class of nanodiamond materials opens new possibilities for surface-modification, for high-efficiency field emitters in molecular electronics, as seed crystals for diamond growth, or as robust mechanical coatings. The properties of self-assembled monolayers (SAMs) of diamondoids are thus of fundamental interest for a variety of emerging applications. This paper presents the effects of thiol substitution position and polymantane order on diamondoid SAMs on gold using nearedge X-ray absorption fine structure spectroscopy (NEXAFS) and X-ray photoelectron spectroscopy (XPS). A framework to determine both molecular tilt and twist through NEXAFS is presented and reveals highly ordered diamondoid SAMs, with the molecular orientation controlled by the thiol location. C 1s and S 2p binding energies are lower in adamantane thiol than alkane thiols on gold by 0.67 ± 0.05 eV and 0.16 ± 0.04 eV respectively. These binding energies vary with diamondoid monolayer structure and thiol substitution position, consistent with different amounts of steric strain and electronic interaction with the substrate. This work demonstrates control over the assembly, in particular the orientational and electronic structure, providing a flexible design of surface properties with this exciting new class of diamond clusters.3

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Section: Introductionmentioning

confidence: 99%

Near-Edge X-ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

et al. 2008

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“…H ighly efficient solar energy harvesting and trapping in photosynthesis relies on sophisticated molecular machinery built from pigment-protein complexes (1,2). Although the pathways and time scales of excitation energy transfers within and among these photosynthetic complexes are well studied, less is known about the precise mechanism responsible for the energy transfer.…”

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Monochromatic Electron Photoemission from Diamondoid Monolayers

Yang

Fabbri

Willey

et al. 2007

Science

262

241

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We found monochromatic electron photoemission from large-area self-assembled monolayers of a functionalized diamondoid, [121]tetramantane-6-thiol. Photoelectron spectra of the diamondoid monolayers exhibited a peak at the low-kinetic energy threshold; up to 68% of all emitted electrons were emitted within this single energy peak. The intensity of the emission peak is indicative of diamondoids being negative electron affinity materials. With an energy distribution width of less than 0.5 electron volts, this source of monochromatic electrons may find application in technologies such as electron microscopy, electron beam lithography, and field-emission flatpanel displays.

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“…Treatment of 8 with NaSH-treated Amberlite, which is reportedly pertinent for some tertiary thiols, 14 was not As an alternative method, Schreiner has demonstrated that tertiary alcohols can be converted to the corresponding thiols by treatment with thiourea in the presence of hydrobromic and acetic acids and subsequent alkaline hydrolysis. 15 The thiolation of monoalcohol 7 gave thiol 9 along with a byproduct alkene 10 (Scheme 4). The selectivity was modified by lowering the temperature of the first step (Table 1), giving an optimal yield of 97% at 25 °C with no detectable formation of the alkene (entry 6).…”

Section: Introductionmentioning

confidence: 99%

Tuning the coverage of self-assembled monolayer by introducing bulky substituents onto rigid adamantane tripod

Kitagawa¹,

Nakanishi²,

Mizuno³

et al. 2017

Arkivoc

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An area-demanding tripodal trithiol containing six peripheral methyl groups was synthesized, and its selfassembled monolayer (SAM) was formed onto a Au(111) surface, which was electrochemically characterized. The SAM showed a significant lowering of the surface coverage due to the bulkiness of the methyl groups, as demonstrated by the charge of reductive elimination. The experimentally determined surface density was aptly reproduced by density functional theory (DFT) calculations under periodic boundary conditions.

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Functionalized Nanodiamonds Part 3: Thiolation of Tertiary/Bridgehead Alcohols

Cited by 76 publications

References 34 publications

Near-Edge X-ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

Near-Edge X-ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

Monochromatic Electron Photoemission from Diamondoid Monolayers

Tuning the coverage of self-assembled monolayer by introducing bulky substituents onto rigid adamantane tripod

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