Absolute configuration of chiral fullerenes and covalent derivatives from their calculated circular dichroism spectra

Gotō, Hitoshi; Harada, Nobuyuki; Crassous, Jeanne; Diederich, François

doi:10.1039/a803689f

Cited by 50 publications

(88 citation statements)

References 21 publications

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“…The applicability of the method was shown, where an excellent agreement with CD measurements in ligand protected nanoclusters, nanotubes, and fullerenes was found [20,41,60]. Using this method the interpretation of the CD spectra of C 76 and C 78 was recently performed [60], improving significantly previous semiempirical calculations [50,51].…”

Section: Fullerenesmentioning

confidence: 85%

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Optically active nanoparticles: Fullerenes, carbon nanotubes, and metal nanoparticles

Hidalgo

Noguez

2010

Physica Status Solidi (b)

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, Phone: þ52 55 5622 5106, Fax: þ52 55 5616 1535A brief topical review of the optical activity of fullerenes, carbon nanotubes, and metallic clusters, is given. Using a recently developed first-principles formalism, the particular case of the optical activity of the chiral C 84 fullerene with D 2 symmetry is studied in detail. In particular, the optical activity of the four possible isomers with this symmetry is studied by calculating the electronic circular dichroism (CD) and compared with experimental data. Although a similar line shape is found for the lowest-energy isomer, the width and intensity of the main experimental peaks are not well reproduced. On the other hand, it is found that the average CD of the mixture of the three lower-energy isomers is in better agreement with experiments. It is expected that this review would be useful as an introduction to optical activity at the nanometer scale, and motivate further experimental studies and the interpretation of natural optical activity in nanoparticles.Calculated CD of a mixture of different isomers of the fullerene C 84 with D 2 symmetry by using DFT and its comparison with experiment.

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Section: Fullerenesmentioning

confidence: 85%

“…After that, optical activity was observed on these fullerenes by measuring CD [48,49]. The interpretation of this chiroptical property in both fullerenes, C 76 and C 78 , was performed using semiempirical calculations [50,51], confirming the existence of chirality on these carbon nanostructures.…”

Section: Fullerenesmentioning

confidence: 93%

Optically active nanoparticles: Fullerenes, carbon nanotubes, and metal nanoparticles

Hidalgo

Noguez

2010

Physica Status Solidi (b)

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“…[47] In 1997 [48] the palmarumycins then provided the first example of a more complex system containing several stereogenic centers (with known relative configuration) that could be stereochemically assigned by quantum chemical CD calculations, while no other methods had, at that time, succeeded in establishing their absolute configurations. Semiempirical methods -CNDO/S, [35] INDO/S, [36] MNDO-based (e.g., OM2), [37] and SCF-CI-DV MO [5] approaches -have been widely applied, and many research groups have used them as tools for the determination of the absolute configurations of a great variety of chiral com-pounds, such as vinblastine alkaloids, by Berova et al, [49] bridged biphenyls, by Sandström, [50] or fullerenes, by Diederich et al [51] In 1997, the concept of UV correction for achieving better agreement between the theoretical UV and CD spectra and the experimentally measured ones, introduced by our group, was a further significant improvement. [9] Many configurational assignments followed, relating mainly to rotationally hindered biaryl axes such as in dioncophylline A [52] or murastifoline F, [53] but also to "molecular chiralities" as in isoplagiochins C and D, [54,55] or to twofold alkylidene-bridged biaryls possessing both planarchiral elements and chiral axes.…”

Section: Semiempirical Methods: Configurational Assignment At the Chimentioning

confidence: 99%

The Assignment of Absolute Stereostructures through Quantum Chemical Circular Dichroism Calculations

et al. 2009

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The determination of the absolute configuration of a chiral compound of synthetic or natural origin is a problem that every organic chemist willl certainly have to face some day. An efficient and reliable method for the assignment of absolute stereostructures, independent of empirical CD rules, is the combination of experimental circular dichroism (CD) investigations with quantum chemical CD calculations. The availability of a broad variety of quantum chemical methods and the continuing appearance of new approaches permits -but also requires -the most appropriate method to be selected in each particular case, with respect to accuracy, time con-

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“…For small chiral molecules containing a single chromophoric group, the electronic circular dichroism can be calculated from first principles using modern quantum chemical methods 16,17 and information can be extracted from the rather subtle CD effects. Aggregates of many chromophoric molecules are systems that are in most cases too large to be amenable to quantum chemical calculations using, e.g., molecular orbital or density functional methods.…”

Section: Introductionmentioning

confidence: 99%

Analysis of the vibronic fine structure in circularly polarized emission spectra from chiral molecular aggregates

Spano

Zhen

Meskers

2004

The Journal of Chemical Physics

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Using a Frenkel-exciton model, the degree of circular polarization of the luminescence (g lum ) from one-dimensional, helical aggregates of chromophoric molecules is investigated theoretically. The coupling between the electronic excitation and a local, intramolecular vibrational mode is taken into account. Analytical expressions for the fluorescence band shape and g lum are presented for the case of strong and weak electronic coupling between the chromophoric units. Results are compared to those from numerical calculations obtained using the three particle approximation. g lum for the 0-0 vibronic band is found to be independent of the relative strength of electronic coupling between chromophores and excitation-vibration coupling. It depends solely on the number of coherently coupled molecules. In contrast, for the higher vibronic transitions ͉g lum ͉ decreases with decreasing strength of the electronic coupling. In the limit of strong electronic coupling, ͉g lum ͉ is almost constant throughout the series of vibronic transitions but for weak coupling ͉g lum ͉ becomes vanishingly small for all vibronic transitions except for the 0-0 transition. The results are interpreted in terms of dynamic localization of the excitation during the zero point vibrational motion in the excited state of the aggregate. It is concluded that circular polarization measurements provide an independent way to determine the coherence size and bandwidth of the lowest exciton state for chiral aggregates.

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Absolute configuration of chiral fullerenes and covalent derivatives from their calculated circular dichroism spectra

Cited by 50 publications

References 21 publications

Optically active nanoparticles: Fullerenes, carbon nanotubes, and metal nanoparticles

Optically active nanoparticles: Fullerenes, carbon nanotubes, and metal nanoparticles

The Assignment of Absolute Stereostructures through Quantum Chemical Circular Dichroism Calculations

Analysis of the vibronic fine structure in circularly polarized emission spectra from chiral molecular aggregates

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