Experimental and Theoretical Study of Dithia[n]metacyclophanes: Syntheses, Chiroptical Properties, and Conformational Analysis

Grimme, Stefan; Pischel, Ivo; Voegtle, F.; Nieger, Martin

doi:10.1021/ja00106a019

Cited by 21 publications

(21 citation statements)

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“…As it has been established by 1 H NMR spectroscopy that for many [5]metacyclophanes a conformational equilibrium between the exo-conformer and the endo-conformer exists 23 (Fig. 2), the structures of both conformers have been optimised for most compounds under investigation in this study.…”

Section: Calculated Structuresmentioning

confidence: 99%

“…Both molecular mechanics (MM2) 3 and semi-empirical (MNDO) 4 techniques have been applied to calculate the structures and strain energies of small [n]metacyclophanes (n = 5, 6, 7), but it was evident that both methods strongly overestimate the out of plane bending of the aromatic ring. So far, ab initio calculations have only been reported by Grimme et al 5 on dithia [6]metacyclophanes, and by Jenneskens et al 6 on [5]metacyclophane. In the latter case, the optimised structure seemed much more realistic than the MNDO structure, although the STO-3G minimal basis SCF method was employed.…”

Section: Introductionmentioning

confidence: 99%

“…In the first place, the evolution of computational chemistry, which has been spurred by the development of ever more powerful CPU's in conjunction with the development of less time demanding calculational methods, like the DF methods, nowadays allows the calculation of large systems using fairly extended basis sets. Secondly, the recent synthesis of derivatives of [5]metacyclophane with sp 2hybridised carbon atoms in the bridge 7,8 prompted us to investigate the influence of unsaturation in the bridge on the structure and strain energy of these compounds. In this way calculations may help to predict whether it is worth pursuing the synthesis of so far elusive compounds such as [1.1]metacyclophane.…”

Section: Introductionmentioning

confidence: 99%

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Structures and strain energies of small [n]metacyclophanes

Eis

Wolf

Bickelhaupt

et al. 2000

J. Chem. Soc., Perkin Trans. 2

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Section: Calculated Structuresmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Structures and strain energies of small [n]metacyclophanes

Eis

Wolf

Bickelhaupt

et al. 2000

J. Chem. Soc., Perkin Trans. 2

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“…The stronger Cotton effect for dithia [7]paracyclophane than for dithia [8]paracyclophane may be ascribed to the difference in deformation angle. [6]metacyclophane (15) and 9,13-dimethyl-2,6-dithia [7]metacyclophane (16) were prepared and their enantiomers were (partially) separated by chiral HPLC (on a Daicel OD column) [26]. The CD spectra of these two metacyclophanes were also investigated by the preliminary theoretical calculations.…”

Section: [N]thiacyclophanesmentioning

confidence: 99%

“…A variety of arenophanes, such as naphthalenophanes, anthracenophanes, fluorenophanes, phenanthrenophanes, and pyrenophanes, have been reported [26]. Among these cyclophanes, chiral azulenophane, 14,17-dimethyl [2](1,3)azuleno [2]paracyclophane (32) has been subjected to repeated theoretical investigations.…”

Section: Metaparacyclophanementioning

confidence: 99%

Recent Theoretical and Experimental Advances in the Electronic Circular Dichroisms of Planar Chiral Cyclophanes

Mori

Inoue

2010

Electronic and Magnetic Properties of Chiral Molecules and Supramolecular Architectures

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The chiroptical properties, such as electronic and vibrational circular dichroism and optical rotation, of planar chiral cyclophanes have attracted much attention in recent years. Although the chemistry of cyclophanes has been extensively explored for more than 60 years, the studies on chiral cyclophanes are rather limited. Experimentally, the use of chiral stationary phases in HPLC becomes more popular and facilitates the enantiomer separation of chiral cyclophanes of interest. Almost all chiral cyclophanes can be readily separated, in analytical and preparative scales, most typically on a Daicel OD type column, which is based on cellulose tris(3,5-dimethylphenylcarbamate). The CD spectra of chiral cyclophanes are unique in their fairly large, significantly coupled Cotton effects observed in all the 1 B b , 1 L a , and 1 L b band regions. Theoretically, the time-dependent density functional theory, or TD-DFT, method becomes a cost-efficient, yet accurate, theoretical method to reproduce the electronic circular dichroisms and the absorption spectra of a variety of cyclophanes. The direct comparison of the experimental CD spectra with the theoretical ones readily leads to the unambiguous assignment of the absolute configuration of cyclophanes. In addition, the analysis of configuration interaction and molecular orbitals allows detailed interpretation of the electronic transitions and Cotton effects in the UV and CD spectra. Through the study of the CD spectra of chiral cyclophanes as model systems, the effects of intra-and intermolecular interactions on the chiroptical properties of molecules can be explored, and the results thus obtained are valuable in comprehensively elucidating the structure-chiroptical property relationship. In this review the recent progress in experimental and theoretical investigations of the electronic CD spectra of chiral cyclophanes is discussed.

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