Hierarchy of Asymmetry at Work: Chain‐Dependent Helix‐to‐Helix Interactions in Supramolecular Polymers

Díaz-Cabrera, Sandra; Dorca, Yeray; Calbo, Joaquín; Aragó, Juan; Gómez, Rafael; Ortı́, Enrique; Sánchez, Luis

doi:10.1002/chem.201706070

Cited by 29 publications

(41 citation statements)

References 34 publications

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“…However, in 2 , the formation of the H‐bonds between the outer amides cancels the conformational freedom of the peripheral units that favors the efficient π‐stacking of the central perylene moiety and, furthermore, the disposition of the external paraphinic chains to interdigitate. The dissimilar packing of the self‐assembling units and the further intertwining of the external chains produce a hierarchical process that finally generates superhelical structures . The results presented herein validate that a fine‐tuned molecular design determines the out‐of‐equilibrium outcome during the supramolecular polymerization and allow stablishing some basic rules about the structural requirements of a self‐assembling unit necessary to experience a efficient SSP that yields supramolecular polymers of controlled size and polydispersity tuning the different hierarchical levels of organization.…”

Section: Figuresupporting

confidence: 60%

Pathway Complexity Versus Hierarchical Self‐Assembly in N‐Annulated Perylenes: Structural Effects in Seeded Supramolecular Polymerization

2018

Self Cite

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Studies were carried out on the hierarchical self‐assembly versus pathway complexity of N‐annulated perylenes 1–3, which differ only in the nature of the linking groups connecting the perylene core and the side alkoxy chains. Despite the structural similarity, compounds 1 and 2 exhibit noticeable differences in their self‐assembly. Whereas 1 forms an off‐pathway aggregate I that converts over time (or by addition of seeds) into the thermodynamic, on‐pathway product, 2 undergoes a hierarchical process in which the kinetically trapped monomer species does not lead to a kinetically controlled supramolecular growth. Finally, compound 3, which lacks the amide groups, is unable to self‐assemble under identical experimental conditions and highlights the key relevance of the amide groups and their position to govern the self‐assembly pathways.

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Section: Figuresupporting

confidence: 60%

Pathway Complexity Versus Hierarchical Self‐Assembly in N‐Annulated Perylenes: Structural Effects in Seeded Supramolecular Polymerization

2018

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“…Helical buckling of the columns (see Figure 2(f)) is entropically favoured for soft columns [23] and can additionally contribute to chirality synchronisation between individual columns and could lead to double-and multi-helical bundles (Figure 2(f-h)). It should be noted that the chirality synchronisation between helical columns is not in all cases enantiophobic (leading to conglomerates), often it is enantiophilic, leading to achiral racemates [220,221].…”

Section: Helical Order In Columnsmentioning

confidence: 99%

Mirror symmetry breaking in liquids and liquid crystals

Tschierske

2018

Liquid Crystals

101

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In the recent two decades liquid crystal science has contributed significantly to the understanding of mirror symmetry breaking and spontaneous emergence of chirality in fluids. This account tries to summarise the current state of understanding of mirror symmetry breaking in the liquid and liquid crystalline mesophases, ranging from isotropic liquids, via cubic, columnar and tetragonal SmQ phases of polycatenar compounds, the twist bend nematic phases of bent dimesogens to the heliconical and conglomerate type smectic phases of bent-core mesogens. Especially, the importance of dynamic chirality synchronisation of molecular conformers, cooperativity, helical superstructures, layer chirality, network formation, as well as chiral and achiral surface effects is discussed. At the end the transition from local to absolute symmetry breaking, chirality amplification and the relevance for the emergence of uniform chirality in prebiotic fluids and biosystems are considered. Dynamic Mirror Symmetry Breaking Transiently chiral molecules Cooperativity Super structural chirality Chirality synchronisation in fluids Network connectivity

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Section: Chirality Creation From An Achiral Unitmentioning

confidence: 99%

Supramolecular Chiral Nanoarchitectonics

et al. 2020

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of well-considered materials designs. [5] Small structural differences in component molecules are often capable of producing materials with totally different properties through organic syntheses, [6] supramolecular chemistry, [7] and materials processing. [8] Therefore, molecular designs for materials production can be regarded as the most important issue in science and technology in current society. Amongst the many possibilities in molecular design for materials production, exploration of molecular functions and material properties on the basis of chirality controls would be a scientifically elegant approach. With identical elemental compositions and functional groups, but different configurations of these identical groups, functions such as chiroptical properties and chiral separations can be created. [9] Another important fact for chiral controls in molecular and materials science is the unavoidable deep relationship of chiral substances with biological activities. [10] Biomolecules are basically made of chiral components such as amino acids and saccharides. Therefore, molecular designs for biomedical drugs and bioactive materials must be produced upon critical control of their chirality. Due to the scientifically elegant approaches and biological importance, molecular sciences and materials technologies incorporating chirality continuously attract attention of scientists ranging from the fundamentals of the chirality of molecules and materials to bio-related applications. These research efforts spread into a wide range of scientific fields including basic physical chemistry, [11] chirality-controlled catalysis and synthesis, [12] chiral materials, [13] analyses of chiral structures, [14] chiral recognition, [15] chiral separation, [16] chiral plasmons and optics, [17] chiral drugs, [18] and biomedical related chiral sciences. [19] Among the broad interests of chirality research, the recent hot trends of chirality related sciences are probably studies on chirality-based supramolecular chemistry and materials science upon the self-assembly of chiral molecular components [20] and achiral building blocks. [21] Enhancement of chiral effects and the creation of chirality are sometimes results of supramolecular organizations with chiral molecular units and even with achiral components. These systems are regarded as elegant examples of the emerging concept of nanoarchitectonics (Figure 1), [22] because control of simple molecular configurations can lead to the creation of such a wide variety of functional materials. The nanoarchitectonics concept was originally proposed by Aono and co-workers [23] as methodology to create functional materials from nanosized components through the combined Exploration of molecular functions and material properties based on the control of chirality would be a scientifically elegant approach. Here, the fabrication and function of chiral-featured materials from both chiral and achiral components using a supramolecular nanoarchitectonics concept are discussed. The contents are classified...

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Hierarchy of Asymmetry at Work: Chain‐Dependent Helix‐to‐Helix Interactions in Supramolecular Polymers

Cited by 29 publications

References 34 publications

Pathway Complexity Versus Hierarchical Self‐Assembly in N‐Annulated Perylenes: Structural Effects in Seeded Supramolecular Polymerization

Pathway Complexity Versus Hierarchical Self‐Assembly in N‐Annulated Perylenes: Structural Effects in Seeded Supramolecular Polymerization

Mirror symmetry breaking in liquids and liquid crystals

Supramolecular Chiral Nanoarchitectonics

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