Autoamplification of Molecular Chirality through the Induction of Supramolecular Chirality

Dijken, Derk Jan van; Beierle, John M.; Stuart, Marc C. A.; Szymański, Wiktor; Browne, Wesley R.; Feringa, Ben L.

doi:10.1002/anie.201311160

Cited by 85 publications

(48 citation statements)

References 43 publications

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“…Particularly, perylene bisimides 18,19 and naphthalene diimides 20,21 are exploited as fluorescent building blocks in construction of these thermodynamically helical nanostructures. Photochromic diarylethenes (DAEs) have also attracted much attention since their chemical and physical properties are reversibly controllable with photo-irradiation [22][23][24] , especially for their functional switching characteristics [25][26][27][28][29][30][31] , such as the photoresponsive helical gel 13,32 and light-driven self-assembly 33,34 . However, the dynamic photoreversibility with modulation of amplified chirality, morphology as well as fluorescence between two thermally stable states are still remaining challenges.…”

Section: Introductionmentioning

confidence: 99%

Enabling Light Work in Helical Self-Assembly for Dynamic Amplification of Chirality with Photoreversibility

et al. 2016

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Light-driven transcription and replication are always subordinate to a delicate chirality transfer. Enabling light work in construction of the helical self-assembly with reversible chiral transformation becomes attractive. Herein we demonstrate that a helical hydrogen-bonded self-assembly is reversibly photoswitched between photochromic open and closed forms upon irradiation with alternative UV and visible light, in which molecular chirality is amplified with the formation of helixes at supramolecular level. The characteristics in these superhelixes such as left-handed or right-handed twist and helical length, height, and pitch are revealed by SEM and AFM. The helical photoswitchable nanostructure provides an easily accessible route to an unprecedented photoreversible modulation in morphology, fluorescence, and helicity, with precise assembly/disassembly architectures similar to biological systems such as protein and DNA.

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Section: Introductionmentioning

confidence: 99%

Enabling Light Work in Helical Self-Assembly for Dynamic Amplification of Chirality with Photoreversibility

et al. 2016

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“…The nanoscale control of chiral molecular assembly at surfaces is of central importance in fields as diverse as chiral separations, 1,2 heterogeneous enantioselective catalysis, 3,4 plasmonics, 5 chiroptical switching 6,7 and biosensors. 8 In all cases, the surface function is profoundly influenced by how individual enantiomers organize at the local and the global level, therefore the outstanding problem in the field is to understand the factors that drive enantiomer assembly and segregation.…”

Section: Introductionmentioning

confidence: 99%

Chiral segregation driven by a dynamical response of the adsorption footprint to the local adsorption environment: bitartrate on Cu(110)

Darling

Forster

Lin

et al. 2017

Phys. Chem. Chem. Phys.

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Local or global ordering of chiral molecules at a surface is a key step in both chiral separation and heterogeneous enantioselective catalysis. Using density functional theory and scanning probe microscopy results, we find that the accepted structural model for the well known bitartrate on Cu(110) chiral system cannot account for the chiral segregation observed. Instead, we show that this strongly bound, chiral adsorbate changes its adsorption footprint in response to the local environment. The flexible adsorption geometry allows bitartrate to form stable homochiral trimer chains in which the central molecule restructures from a rectangular to an oblique footprint, breaking its internal hydrogen bonds in order to form strong intermolecular hydrogen bonds to neighbouring adsorbates. Racemic structures containing mixed enantiomers do not form strong hydrogen bonds, providing the thermodynamic driving force for the chiral separation that is observed experimentally. This result shows the importance of considering the dynamical response of molecular adsorption footprints at the surface in directing chiral assembly and segregation. The ability of strongly-chemisorbed enantiomers to change footprint depending on the local adsorption environment indicates that supramolecular assemblies at surfaces may exhibit more complex dynamical behaviour than hitherto suspected, which, ultimately, could be tailored to lead to environment and stimuli-responsive chiral surfaces.

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“…Nonetheless, the flexibility of aryl groups and their fast rotation in the ring‐open isomer lead to the inevitable racemization during the photochromic reaction. Methods like covalently linking two reaction sites, self‐assembly via gel‐formation or taking advantage of the chirality of certain proteins, have been applied to control the handiness of the open isomer enantiomers and improved the e.e . value after the photocyclization (see the following section for details).…”

Section: Designing New Members For Diarylethene Familymentioning

confidence: 99%

“…Upon the noncovalent interactions and regular self‐assembly between gelators, gels provide confined spaces and constrained binding for both gelator molecules and “accommodating” molecules, either small molecules or macromolecules, even cells . Taking advantage of this feature, Feringa and co‐workers amplified the inherent chirality of diarylethenes through the induction of supramolecular chirality of a supramolecular photochromic gel . An amide linked diarylethene was synthesized which could form intermolecular hydrogen bonding and self‐assemble into a gel.…”

Section: Applications Of Diarylethene Based Materialsmentioning

confidence: 99%

The Endeavor of Diarylethenes: New Structures, High Performance, and Bright Future

Zhang

Tian

2018

Advanced Optical Materials

206

127

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Photochromism is a term that describes the photoreversible isomerization between two different states or isomers with distinct performances. Among all the photochromic molecule family, diarylethene is considered one of the most popular star molecules on account of its fast photoresponsibility, excellent thermal stability, fatigue resistance, high photoreaction quantum yield, and conversion ratio as well as good performances in both solution and solid phases. In the past decades, the development of diarylethene is witnessed in molecule design, solution applications, surface/interface assembly, bulky crystals and polymers, optic‐electronic devices fabrication, and biotechnology. This review mainly focuses on the latest development of diarylethenes in recent five years and commences with the newly designed molecular structures with functional ethene bridges and aryl moieties. The application of diarylethenes in materials science, soft materials, molecular data processing, and biomaterials, is further discussed in prospect. A brief summary is given in the end of the review together with some perspectives.

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Autoamplification of Molecular Chirality through the Induction of Supramolecular Chirality

Cited by 85 publications

References 43 publications

Enabling Light Work in Helical Self-Assembly for Dynamic Amplification of Chirality with Photoreversibility

Enabling Light Work in Helical Self-Assembly for Dynamic Amplification of Chirality with Photoreversibility

Chiral segregation driven by a dynamical response of the adsorption footprint to the local adsorption environment: bitartrate on Cu(110)

The Endeavor of Diarylethenes: New Structures, High Performance, and Bright Future

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