[123]Tetramantane: Parent of a New Family of σ-Helicenes

Schreiner, Peter R.; Fokin, Andrey A.; Reisenauer, Hans Peter; Tkachenko, Boryslav A.; Vass, Elemér; Olmstead, Marilyn M.; Bläser, Dieter; Boese, Roland; Dahl, Jeremy E. P.; Carlson, Robert M. K.

doi:10.1021/ja904527g

Cited by 45 publications

(133 citation statements)

References 29 publications

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“…The high density of vibrational states, the presence of several hot bands, and the numerous possible anharmonic interactions prevented us from resolving the rotational structure in this part of the spectrum. Table III lists In the following paragraphs we present the first rotational analysis and fit of 7 fundamental bands of adamantane: ν 23 , ν 24 , ν 25 , ν 26 , ν 27 , ν 28 , and ν 30 . For the spectral analysis, it is possible to use the tools that have been developed previously for smaller tetrahedral molecules, importantly CH 4 .…”

Section: Resultsmentioning

confidence: 99%

“…As we show below, ν 30 , ν 28 , ν 27 , ν 26 , and ν 23 can be treated as isolated bands. In contrast, ν 25 and ν 24 should be treated as a dyad, with a strong Coriolis interaction between the two bands. Figure 3 shows the high resolution spectra of the ν 30 , ν 28 , ν 27 , ν 26 , ν 23 bands and Fig.…”

Section: Resultsmentioning

confidence: 99%

“…23 Furthermore, chiral properties of higher diamondoid molecules, as well as of halogenated adamantane have been studied with optical rotation and vibrational circular dichroism (CD and VCD) spectroscopy. 24,25 Since adamantane is a tetrahedral molecule, it has no permanent dipole moment in its vibronic ground state, so that no pure rotational spectrum exists; moreover, to our knowledge, rotationally resolved IR or UV/vis spectra have not been reported to date for any diamondoid molecule, so that no experimental information on the rotational structure is available whatsoever.…”

Section: Introductionmentioning

confidence: 99%

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Rotationally resolved infrared spectroscopy of adamantane

Pirali

Boudon

Oomens

et al. 2012

The Journal of Chemical Physics

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Rotationally resolved infrared spectroscopy of adamantanePirali, O.; Boudon, V.; Oomens, J.; Vervloet, M. General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. We present the first rotationally resolved spectra of adamantane (C 10 H 16 ) applying gas-phase Fourier transform infrared (IR) absorption spectroscopy. High-resolution IR spectra are recorded in the 33-4500 cm −1 range using as source of IR radiation both synchrotron radiation (at the AILES beamline of the SOLEIL synchrotron) as well as a classical globar. Adamantane is a spherical top molecule with tetrahedral symmetry (T d point group) and has no permanent dipole moment in its vibronic ground state. Of the 72 fundamental vibrational modes in adamantane, only 11 are IR active. Here we present rotationally resolved spectra for seven of them: ν 30 , ν 28 , ν 27 , ν 26 , ν 25 , ν 24 , and ν 23 . The typical rotational structure of spherical tops is observed and analyzed using the STDS software developed in the Dijon group, which provides the first accurate energy levels and rotational constants for seven fundamental modes. Rotational levels with quantum numbers as high as J = 107 have been identified and included in the fit leading to a typical standard deviation of about 10 −3 cm −1 .

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Rotationally resolved infrared spectroscopy of adamantane

Pirali

Boudon

Oomens

et al. 2012

The Journal of Chemical Physics

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“…17 Using optical rotatory dispersion and vibrational circular dichroism spectroscopy, the chirality of [123]tetramantane was observed. 18 A study of the structure of the adamantane cation 19 provides evidence of a Jahn-Teller distortion in the cationic electronic ground state. Size-and shape-selected neutral diamondoids in the gas phase are optimal model systems for theory, especially for the study of quantum confinement effects.…”

Section: Introductionmentioning

confidence: 99%

Laser-induced fluorescence of free diamondoid molecules

Richter

Röhr

Zimmermann

et al. 2015

Phys. Chem. Chem. Phys.

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aWe observe the fluorescence of pristine diamondoids in the gas phase, excited using narrow band ultraviolet laser light. The emission spectra show well-defined features, which can be attributed to transitions from the excited electronic state into different vibrational modes of the electronic ground state. We assign the normal modes responsible for the vibrational bands, and determine the geometry of the excited states. Calculations indicate that for large diamondoids, the spectral bands do not result from progressions of single modes, but rather from combination bands composed of a large number of Dv = 1 transitions. The vibrational modes determining the spectral envelope can mainly be assigned to wagging and twisting modes of the surface atoms. We conclude that our theoretical approach accurately describes the photophysics in diamondoids and possibly other hydrocarbons in general.

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“…Functionalized diamondoids obtained by regioselective reactions offer a wide range of possible shapes in three dimensions. [14][15][16]21,22 In order to specify the location and stereochemistry of substituents, the von Baeyer nomenclature enhanced by stereochemical descriptors as advocated here is the best available system.…”

Section: Stereochemical Aspects In Perimantanes That Have As Dualistsmentioning

confidence: 99%

Helical [n]catamantanes and all-trans-perhydroacenic [n]perimantanes: structures and von Baeyer IUPAC numbering of carbon atoms

Balaban¹,

Rücker²

2013

Arkivoc

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Abstract[n]Diamondoids are hydrocarbons whose carbon skeleton is a portion of the diamond lattice, and contains n adamantane cells (or units) sharing chair-shaped hexagons of carbon atoms. When centers of these adamantane units are connected by lines, the resulting construction is called the dualist of the diamondoid, and it also is similar to a portion of the diamond lattice. While these hydrocarbons can be distinguished by the Balaban-Schleyer nomenclature system, substituted derivatives are to be described by the IUPAC von Baeyer nomenclature that attributes a unique number (locant) to each carbon atom within a molecule. In this paper, von Baeyer names and corresponding atom numberings were obtained by the computer program POLCYC for members of two classes of diamondoids: [n]catamantanes whose dualists are tight helices, and [n]perimantanes whose dualists are all-trans-perhydroacenes; general numbering schemes were derived for these compound classes. The structures and some regularities in their structural properties are discussed.

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[123]Tetramantane: Parent of a New Family of σ-Helicenes

Cited by 45 publications

References 29 publications

Rotationally resolved infrared spectroscopy of adamantane

Rotationally resolved infrared spectroscopy of adamantane

Laser-induced fluorescence of free diamondoid molecules

Helical [n]catamantanes and all-trans-perhydroacenic [n]perimantanes: structures and von Baeyer IUPAC numbering of carbon atoms

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