Asymmetric and fused heterocycles based on [2.2]paracyclophane

Aly, Ashraf A.; Brown, Alan B.

doi:10.1016/j.tet.2009.06.034

Cited by 100 publications

(34 citation statements)

References 184 publications

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“…The |De| values at the main band (40-70 M -1 cm -1 ) are large relative to those of nonoxa- [7]paracyclophane 4 [19]. It is to note that the calculated deformation angle of [7]cyclophane 5 is similar to those of [2.2]paracyclophanes. The theoretical study has been updated by using the more recent TD-DFT method at the B3-LYP/TZV2P 0 level and all of the four resolved bands in the experimental CD spectra were very well reproduced [8].…”

Section: [N]paracyclophanesmentioning

confidence: 74%

“…The observed Cotton effects were slightly weaker than those observed for [6]paracyclophane 2 [18]. The CD spectrum of 9,12-dimethyl-4-oxa [7]paracyclophane 5 was measured and compared with the theoretical one calculated with the DFT/SCI method. The |De| values at the main band (40-70 M -1 cm -1 ) are large relative to those of nonoxa- [7]paracyclophane 4 [19].…”

Section: [N]paracyclophanesmentioning

confidence: 93%

“…The CD spectra of enantiomerically enriched [7]paracyclophane 4 was also reported. The observed Cotton effects were slightly weaker than those observed for [6]paracyclophane 2 [18].…”

Section: [N]paracyclophanesmentioning

confidence: 99%

“…The CD spectrum of 9,12-dimethyl-4-oxa [7]paracyclophane 5 was measured and compared with the theoretical one calculated with the DFT/SCI method. The |De| values at the main band (40-70 M -1 cm -1 ) are large relative to those of nonoxa- [7]paracyclophane 4 [19]. It is to note that the calculated deformation angle of [7]cyclophane 5 is similar to those of [2.2]paracyclophanes.…”

Section: [N]paracyclophanesmentioning

confidence: 99%

“…Recent advances and applications in this area have been reviewed [5,6]. The synthesis of heterocyclic compounds based on [2.2]paracyclophane architecture, where the long-distance electronic communication and the planar chirality play significant roles in their application, has also been reported recently [7]. Although the preparation and application of chiral cyclophanes in asymmetric synthesis has attracted much attention for a long time, their chiroptical properties, especially the CD spectra, have rarely been paid attention or even completely ignored.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

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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Section: [N]paracyclophanesmentioning

confidence: 74%

Section: [N]paracyclophanesmentioning

confidence: 93%

“…The CD spectra of enantiomerically enriched [7]paracyclophane 4 was also reported. The observed Cotton effects were slightly weaker than those observed for [6]paracyclophane 2 [18].…”

Section: [N]paracyclophanesmentioning

confidence: 99%

Section: [N]paracyclophanesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

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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Planar Chiral [2.2]Paracyclophane: Excellent Circularly Polarized Luminescence Emitters

Morisaki

2024

Chiral Luminescence

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Optically Active A‐Shaped Cyclic Molecules Based on Planar Chiral [2.2]Paracyclophanes Emitting Bright Circularly Polarized Luminescence with High Anisotropy Factors

Matsumura,

Inoue,

Morisaki

2023

Adv Funct Materials

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Optically active A‐shaped cyclic molecules are synthesized by incorporating a planar chiral [2.2]paracyclophane unit to form a helical structure. These molecules exhibit large molar absorption coefficients, moderate photoluminescence (PL) quantum efficiencies, and high circularly polarized luminescence (CPL) anisotropy factors, resulting in high CPL brightness values (BCPL values). According to the time‐dependent density functional theory (TD‐DFT) theoretical studies, extended π‐conjugated moieties act as light‐harvesting units, and emissions occur from the helical skeletons. The TD‐DFT calculations reproduce the experimentally determined absorption, PL, circular dichroism, and CPL properties of the A‐shaped cyclic molecules.

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Asymmetric and fused heterocycles based on [2.2]paracyclophane

Cited by 100 publications

References 184 publications

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

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

Planar Chiral [2.2]Paracyclophane: Excellent Circularly Polarized Luminescence Emitters

Optically Active A‐Shaped Cyclic Molecules Based on Planar Chiral [2.2]Paracyclophanes Emitting Bright Circularly Polarized Luminescence with High Anisotropy Factors

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