Stepwise elaboration of diamondoid hydrocarbons. Synthesis of diamantane from adamantane

Fǎrcaşiu, D.; Bohm, Howard; Schleyer, Paul v. R.

doi:10.1021/jo00421a018

Cited by 15 publications

(10 citation statements)

References 6 publications

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“…They comprise a relatively novel class of molecules with a variety of potential applications in biochemistry, pharmaceutical sciences and nanotechnology. [5][6] Nanodiamonds not only hold important promise for practical use, but also likely play an important role in star formation and the evolution of interstellar matter due to their remarkable stability. Small nanodiamonds occur naturally and are found in hydrocarbon mixtures such as crude oil and natural gas and can be isolated from those resources, [3][4] but they can also be synthesized by a variety of methods.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic Characterization of the Product Ions Formed by Electron Ionization of Adamantane

Bouwman

Horst

2018

ChemPhysChem

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A structural characterization of the products formed in the dissociative electron ionization of adamantane (C 10 H 16 ) is presented. Molecular structures of product ions are suggested based on multiple‐photon dissociation spectroscopy using the Free Electron Laser for Infrared eXperiments (FELIX) in combination with quantum‐chemical calculations. Product ions are individually isolated in an ion trap tandem mass spectrometer and their action IR spectra are recorded. Atomic hydrogen loss from adamantane yields the 1‐adamantyl isomer. The IR spectrum of the C 8 H 11 + product ion is best reproduced by computed spectra of 2‐ and 4‐protonated meta ‐xylene and ortho ‐ and para‐ protonated ethylbenzenes. The spectrum of the product ion at m/z 93 suggests that it is composed of a mixture of ortho ‐protonated toluene, para ‐protonated toluene and 1,2‐dihydrotropylium, while the spectrum of the m/z 79 ion is consistent with the benzenium ion. This study thus suggests that adamantane is efficiently converted into aromatic species and astrophysical implications for the interstellar medium are highlighted.

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Section: Introductionmentioning

confidence: 99%

Spectroscopic Characterization of the Product Ions Formed by Electron Ionization of Adamantane

Bouwman

Horst

2018

ChemPhysChem

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“…Higher diamondoids, larger than triamantane (C 18 H 24 ), have never been synthesized (FarcaYiu et al 1977). However, molecular diamondoids as large as undecamantane were recently isolated from crude oil ( Dahl et al 2003).…”

Section: Introductionmentioning

confidence: 99%

Infrared Spectroscopy of Diamondoid Molecules: New Insights into the Presence of Nanodiamonds in the Interstellar Medium

Pirali

Vervloët

Dahl

et al. 2007

ApJ

112

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Although they are relatively different in band shape, infrared features around 3.4-3.5 m in the emission spectra of HD 97048 and Elias 1 and in the absorption spectra of various dense clouds have both been attributed to diamondoid molecules /particles. This assignment is based mainly on infrared spectra of hydrogenated diamond thin films and of diamond nanocrystals of known average size. Here we present an analysis of the astrophysical implications of recently reported solid-state 2.5-12.5 m spectra of individual diamondoid molecules, up to the size of hexamantane (C 26 H 30 ). These spectra provide the first experimental measurements of the infrared frequencies of this class of molecules. In addition, laboratory gas-phase infrared emission spectra of the three smallest members of the diamondoid family are reported, as well as theoretical spectra for some larger species. The present data set allows us to relate spectral signatures to the molecular size and structure. The spectra of tetrahedral diamondoids are found to be qualitatively different from those of lower symmetry species, which possibly explains the differences between the astrophysical emission and absorption spectra. Interestingly, the 3.53 m band is clearly observed in the spectra of these small molecular diamondoids, whereas previous studies on nanodiamond particles found this band only for species larger than %50 nm. Our results support the assignment of the 3.43 and 3.53 m emission features in HD 97048 and Elias 1 to diamondoids of a few nanometers in size as well as the suggestion that smaller diamondoid molecules contribute to the 3.47 m interstellar absorption band.

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“…[169] In comparison to other polymer "additives" the role of diamondoids is not fully explored but the present results show that polymantanes (especially the functionalized ones) will probably give rise to materials with the above mentioned desirable properties. The thiol derivatives of 4 b and 5, such as anti-tetramantane-6-thiol (58), can be attached to gold surfaces (Figure 2 top). [78] Another interesting combination consists of the two different pentamantane thiol derivatives 59 and 60, because of their "trigonal-pyramidal shape" which would result in the surface being totally covered by a tight packing of diamondoids (Figure 2 bottom).…”

Section: Methodsmentioning

confidence: 99%

“…[57] Another pathway is the stepwise elaboration from 1 developed by Fǎ rcaşiu et al in 1977. [58] This method is in principle a route to synthesize even higher diamondoids but it is not practical owing to the many steps required. Takhistov et al used phenylcyclopentane and phenylcyclohexane to prepare methyl and dimethyldiamantanes.…”

Section: Origin and Synthesis Of Diamondoidsmentioning

confidence: 99%

Diamonds are a Chemist's Best Friend: Diamondoid Chemistry Beyond Adamantane

2008

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Marilyn Monroe knew that "diamonds are a girl's best friend" but, in the meantime, many chemists have realized that they are also extremely attractive objects in contemporary chemistry. The chemist's diamonds are usually quite small (herein: nanometer-sized "diamondoids") and as a result of their unique structure are unusual chemical building blocks. Since lower diamondoids (up to triamantane) have recently become available in large amounts from petroleum and higher diamondoids (starting from tetramantane) are now also accessible from crude oil new research involving them has begun to emerge. Having well-defined structures makes these cage compounds so special compared to other nanometer-scale diamonds. Selective and high-yielding synthetic approaches to the functionalization of diamondoids gives derivatives that can find applications in, for example, polymers, coating materials, drugs, and molecular electronics.

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Stepwise elaboration of diamondoid hydrocarbons. Synthesis of diamantane from adamantane

Cited by 15 publications

References 6 publications

Spectroscopic Characterization of the Product Ions Formed by Electron Ionization of Adamantane

Spectroscopic Characterization of the Product Ions Formed by Electron Ionization of Adamantane

Infrared Spectroscopy of Diamondoid Molecules: New Insights into the Presence of Nanodiamonds in the Interstellar Medium

Diamonds are a Chemist's Best Friend: Diamondoid Chemistry Beyond Adamantane

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