Diastereoisomerically Pure Fulleropyrrolidines as Chiral Platforms for the Design of Optically Active Liquid Crystals

Stephane Campidelli; Philippe Bourgun; Boris Guintchin; Julien Furrer; Helen Stoeckli-Evans; Isabel M. Saez; John W. Goodby; Robert Deschenaux

doi:10.1021/ja910128e

Diastereoisomerically Pure Fulleropyrrolidines as Chiral Platforms for the Design of Optically Active Liquid Crystals

Stephane Campidelli, Philippe Bourgun, Boris Guintchin, Julien Furrer, Helen Stoeckli-Evans, Isabel M. Saez, John W. Goodby, Robert Deschenaux

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Incorporation of [60]fullerene (C-60) within self-organizing systems is conceptually challenging but allows us to obtain materials which combine the characteristics (anisotropy, organization) of condensed mesophases with the properties of C-60 (photo- and electrochemical activity). Here, we report on the synthesis, characterization, and liquid-crystalline properties of four optically active fullerodendrimers, which are chiral at the point of conjunction between the fullerene scaffold and the mesogenic moieties. Thus, the novelty of this study is to take advantage of the asymmetric carbon atom created during the 1,3-dipolar cycloaddition reaction on C-60 in order to induce mesoscopic chirality in the materials. Four diastereoisomeric fulleropyrrolidines ((R,S)-1, (R,R)-1, (S,R)-1, and (S,S)-1) were synthesized and associated with a second-generation nematic (N) dendron to give fullerodendrimers ((R,S)-2, (R,R)-2, (S,R)-2, and (S,S)-2) which display chiral nematic (N*) phases. The absolute configurations of the stereogenic centers were determined by X-ray crystallography, 1D and 2D NMR experiments, and circular dichroism (CD) spectroscopy. The liquid-crystalline properties of the fullerodendrimers were studied by polarized optical microscopy (POM) and differential scanning calorimetry (DSC). The fulleropyrrolidine derivatives 2 exhibit supramolecular helicoidal organizations with a right-handed helix for the (R,S)-2 and (R,R)-2 diastereoisomers and a left-handed helix for the (S,R)-2 and (S,S)-2 diastereoisomers. This result suggests that the self-organization of such supermolecular materials can be controlled at the molecular level by the introduction of only one chiral center.

Original language	English
Pages (from-to)	3574-3581
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	132
Issue number	10
DOIs	https://doi.org/10.1021/ja910128e
Publication status	Published - 17 Mar 2010

Keywords

FULLERENE-FERROCENE DYADS
SELF-ORGANIZATION
DENDRITIC MACROMOLECULES
CONVERGENT APPROACH
DERIVATIVES
FULLERODENDRIMERS
DENDRIMERS
COLUMNAR
TEMPERATURE
BEHAVIOR

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10.1021/ja910128e

http://pubs.acs.org/doi/abs/10.1021/ja910128e

Cite this

@article{66a8501db73348afa618cfa27b839754,

title = "Diastereoisomerically Pure Fulleropyrrolidines as Chiral Platforms for the Design of Optically Active Liquid Crystals",

abstract = "Incorporation of [60]fullerene (C-60) within self-organizing systems is conceptually challenging but allows us to obtain materials which combine the characteristics (anisotropy, organization) of condensed mesophases with the properties of C-60 (photo- and electrochemical activity). Here, we report on the synthesis, characterization, and liquid-crystalline properties of four optically active fullerodendrimers, which are chiral at the point of conjunction between the fullerene scaffold and the mesogenic moieties. Thus, the novelty of this study is to take advantage of the asymmetric carbon atom created during the 1,3-dipolar cycloaddition reaction on C-60 in order to induce mesoscopic chirality in the materials. Four diastereoisomeric fulleropyrrolidines ((R,S)-1, (R,R)-1, (S,R)-1, and (S,S)-1) were synthesized and associated with a second-generation nematic (N) dendron to give fullerodendrimers ((R,S)-2, (R,R)-2, (S,R)-2, and (S,S)-2) which display chiral nematic (N*) phases. The absolute configurations of the stereogenic centers were determined by X-ray crystallography, 1D and 2D NMR experiments, and circular dichroism (CD) spectroscopy. The liquid-crystalline properties of the fullerodendrimers were studied by polarized optical microscopy (POM) and differential scanning calorimetry (DSC). The fulleropyrrolidine derivatives 2 exhibit supramolecular helicoidal organizations with a right-handed helix for the (R,S)-2 and (R,R)-2 diastereoisomers and a left-handed helix for the (S,R)-2 and (S,S)-2 diastereoisomers. This result suggests that the self-organization of such supermolecular materials can be controlled at the molecular level by the introduction of only one chiral center.",

keywords = "FULLERENE-FERROCENE DYADS, SELF-ORGANIZATION, DENDRITIC MACROMOLECULES, CONVERGENT APPROACH, DERIVATIVES, FULLERODENDRIMERS, DENDRIMERS, COLUMNAR, TEMPERATURE, BEHAVIOR",

author = "Stephane Campidelli and Philippe Bourgun and Boris Guintchin and Julien Furrer and Helen Stoeckli-Evans and Saez, {Isabel M.} and Goodby, {John W.} and Robert Deschenaux",

year = "2010",

month = mar,

day = "17",

doi = "10.1021/ja910128e",

language = "English",

volume = "132",

pages = "3574--3581",

journal = "Journal of the American Chemical Society",

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publisher = "American Chemical Society",

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T1 - Diastereoisomerically Pure Fulleropyrrolidines as Chiral Platforms for the Design of Optically Active Liquid Crystals

AU - Campidelli, Stephane

AU - Bourgun, Philippe

AU - Guintchin, Boris

AU - Furrer, Julien

AU - Stoeckli-Evans, Helen

AU - Saez, Isabel M.

AU - Goodby, John W.

AU - Deschenaux, Robert

PY - 2010/3/17

Y1 - 2010/3/17

N2 - Incorporation of [60]fullerene (C-60) within self-organizing systems is conceptually challenging but allows us to obtain materials which combine the characteristics (anisotropy, organization) of condensed mesophases with the properties of C-60 (photo- and electrochemical activity). Here, we report on the synthesis, characterization, and liquid-crystalline properties of four optically active fullerodendrimers, which are chiral at the point of conjunction between the fullerene scaffold and the mesogenic moieties. Thus, the novelty of this study is to take advantage of the asymmetric carbon atom created during the 1,3-dipolar cycloaddition reaction on C-60 in order to induce mesoscopic chirality in the materials. Four diastereoisomeric fulleropyrrolidines ((R,S)-1, (R,R)-1, (S,R)-1, and (S,S)-1) were synthesized and associated with a second-generation nematic (N) dendron to give fullerodendrimers ((R,S)-2, (R,R)-2, (S,R)-2, and (S,S)-2) which display chiral nematic (N*) phases. The absolute configurations of the stereogenic centers were determined by X-ray crystallography, 1D and 2D NMR experiments, and circular dichroism (CD) spectroscopy. The liquid-crystalline properties of the fullerodendrimers were studied by polarized optical microscopy (POM) and differential scanning calorimetry (DSC). The fulleropyrrolidine derivatives 2 exhibit supramolecular helicoidal organizations with a right-handed helix for the (R,S)-2 and (R,R)-2 diastereoisomers and a left-handed helix for the (S,R)-2 and (S,S)-2 diastereoisomers. This result suggests that the self-organization of such supermolecular materials can be controlled at the molecular level by the introduction of only one chiral center.

AB - Incorporation of [60]fullerene (C-60) within self-organizing systems is conceptually challenging but allows us to obtain materials which combine the characteristics (anisotropy, organization) of condensed mesophases with the properties of C-60 (photo- and electrochemical activity). Here, we report on the synthesis, characterization, and liquid-crystalline properties of four optically active fullerodendrimers, which are chiral at the point of conjunction between the fullerene scaffold and the mesogenic moieties. Thus, the novelty of this study is to take advantage of the asymmetric carbon atom created during the 1,3-dipolar cycloaddition reaction on C-60 in order to induce mesoscopic chirality in the materials. Four diastereoisomeric fulleropyrrolidines ((R,S)-1, (R,R)-1, (S,R)-1, and (S,S)-1) were synthesized and associated with a second-generation nematic (N) dendron to give fullerodendrimers ((R,S)-2, (R,R)-2, (S,R)-2, and (S,S)-2) which display chiral nematic (N*) phases. The absolute configurations of the stereogenic centers were determined by X-ray crystallography, 1D and 2D NMR experiments, and circular dichroism (CD) spectroscopy. The liquid-crystalline properties of the fullerodendrimers were studied by polarized optical microscopy (POM) and differential scanning calorimetry (DSC). The fulleropyrrolidine derivatives 2 exhibit supramolecular helicoidal organizations with a right-handed helix for the (R,S)-2 and (R,R)-2 diastereoisomers and a left-handed helix for the (S,R)-2 and (S,S)-2 diastereoisomers. This result suggests that the self-organization of such supermolecular materials can be controlled at the molecular level by the introduction of only one chiral center.

KW - FULLERENE-FERROCENE DYADS

KW - SELF-ORGANIZATION

KW - DENDRITIC MACROMOLECULES

KW - CONVERGENT APPROACH

KW - DERIVATIVES

KW - FULLERODENDRIMERS

KW - DENDRIMERS

KW - COLUMNAR

KW - TEMPERATURE

KW - BEHAVIOR

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U2 - 10.1021/ja910128e

DO - 10.1021/ja910128e

M3 - Article

SN - 0002-7863

VL - 132

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EP - 3581

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 10

ER -

Diastereoisomerically Pure Fulleropyrrolidines as Chiral Platforms for the Design of Optically Active Liquid Crystals

Abstract

Keywords

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