Towards supramolecular nanostructured materials: control of the self-assembly of ionic bent-core amphiphiles

Castillo-Vallés, Martín; Cano, Miguel; Bermejo-Sanz, Ana María; Gimeno, Nélida; Ros, M. Blanca

doi:10.1039/c9tc06002b

Cited by 15 publications

(11 citation statements)

References 88 publications

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“…Considering this lack of consistent heliconical layering observed for 2 , one could interpret this as a visual indication that elongation of aliphatic chains with a chiral center at the core-chain juncture diminishes the effects of the chiral center and that this results in the largely observed lack of heliconical layering or a significant increase in the helical pitch p . Related cylinder or tubular superstructures with no evidence of heliconical layering were reported by others previously for achiral bent-core compounds in colloidal dispersions (gels) using organic solvents , or in the case of ionic bent-core materials after self-assembly in water …”

Section: Results and Discussionsupporting

confidence: 70%

Molecular Conformation of Bent-Core Molecules Affected by Chiral Side Chains Dictates Polymorphism and Chirality in Organic Nano- and Microfilaments

et al. 2021

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The coupling between molecular conformation and chirality is a cornerstone in the construction of supramolecular helical structures of small molecules across various length scales. Inspired by biological systems, conformational preselection and control in artificial helical molecules, polymers, and aggregates has guided various applications in optics, photonics, and chiral sorting among others, which are frequently based on an inherent chirality amplification through processes such as templating and self-assembly. The so-called B4 nano- or microfilament phase formed by some bent-shaped molecules is an exemplary case for such chirality amplification across length scales, best illustrated by the formation of distinct nano- or microscopic chiral morphologies controlled by molecular conformation. Introduction of one or more chiral centers in the aliphatic side chains led to the discovery of homochiral helical nanofilament, helical microfilament, and heliconical-layered nanocylinder morphologies. Herein, we demonstrate how a priori calculations of the molecular conformation affected by chiral side chains are used to design bent-shaped molecules that self-assemble into chiral nano- and microfilament as well as nanocylinder conglomerates despite the homochiral nature of the molecules. Furthermore, relocation of the chiral center leads to formation of helical as well as flat nanoribbons. Self-consistent data sets from polarized optical as well as scanning and transmission electron microscopy, thin-film and solution circular dichroism spectropolarimetry, and synchrotron-based X-ray diffraction experiments support the progressive and predictable change in morphology controlled by structural changes in the chiral side chains. The formation of these morphologies is discussed in light of the diminishing effects of molecular chirality as the chain length increases or as the chiral center is moved away from the core-chain juncture. The type of phase (B1-columnar or B4) and morphology of the nano- or microfilaments generated can further be controlled by sample treatment conditions such as by the cooling rate from the isotropic melt or by the presence of an organic solvent in the ensuing colloidal dispersions. We show that these nanoscale morphologies can then organize into a wealth of two- and three-dimensional shapes and structures ranging from flower blossoms to fiber mats formed by intersecting flat nanoribbons.

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Section: Results and Discussionsupporting

confidence: 70%

Molecular Conformation of Bent-Core Molecules Affected by Chiral Side Chains Dictates Polymorphism and Chirality in Organic Nano- and Microfilaments

et al. 2021

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“…These materials gave rise to a wide range of nanostructures (rods, non-twisted or twisted bres, helical ribbons and nanotubes) in which compact packing that characterises bent-core mesophases was also present. 4,5 Interestingly, these results offer innovative possibilities for bent-core based associations.…”

Section: Introductionmentioning

confidence: 91%

“…This methodology, a conventional batch synthesis, involves the dropwise addition of water (poor solvent) to an organic solution that contains an amphiphile, 29 an approach that has proven to be an easy procedure for the fabrication of nanostructures from bent-core based dendrimers in previous studies. 4,5 However, the co-solvent method is time-consuming and concentration gradients are formed as the water content is higher in the locations where the drop comes into contact with the organic phase. In contrast, micro-uidic devices allow uid ows to be handled at the microscale very precisely and this leads to highly reproducible syntheses and mixing conditions.…”

Section: Processing Conditionsmentioning

confidence: 99%

Microfluidics for the rapid and controlled preparation of organic nanotubes of bent-core based dendrimers

et al. 2021

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“…The implementation of double-tail dialkyl phosphate surfactants layers in conjugated oligoanilines by spontaneous electrostatic self-assembly (without a layer-by-layer technique) allowed a temperature-controlled switchability of the films due to disorder ( Wei et al, 2005 ). Meanwhile a wide variety of such materials exists, including the use of supramolecular metallo-polyelectrolytes with surfactants ( Kurth et al, 2000 ), or small ionic dendrimers with surfactants ( Hernández-Ainsa et al, 2011 ; Castillo-Vallés et al, 2020 ).…”

Section: Spontaneous Electrostatic Self-assemblymentioning

confidence: 99%

“…In some cases, the association of small ionic dendrimers with surfactants can lead to amphiphile assemblies in aqueous solution rather than the macroscopic materials outlined in Section 4.3. Typical amphiphile assemblies such as micelles and vesicles result with common surfactants, while helices were created with an ionic bent amphiphile containing a bent aromatic moiety between head and tail group (Hernández-Ainsa et al, 2011;Castillo-Vallés et al, 2020). In a different system, the Keggin-type polyoxotungstates SiW 12 O 4 4− with four negative charges build onion-like layered spherical architectures with cationic dimethyldioctadecylammonium surfactants, as shown by Sun et al (Li et al, 2007) The group of Tianbu Liu explored the interaction of a type of "Keplerate" polyoxometalate macroanionic clusters with cationic surfactants.…”

Section: Structural Variety Of Supramolecular Assemblies In Solutionmentioning

confidence: 99%

Functional Nano-Objects by Electrostatic Self-Assembly: Structure, Switching, and Photocatalysis

2022

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The design of functional nano-objects by electrostatic self-assembly in solution signifies an emerging field with great potential. More specifically, the targeted combination of electrostatic interaction with other effects and interactions, such as the positioning of charges on stiff building blocks, the use of additional amphiphilic, π−π stacking building blocks, or polyelectrolytes with certain architectures, have recently promulgated electrostatic self-assembly to a principle for versatile defined structure formation. A large variety of architectures from spheres over rods and hollow spheres to networks in the size range of a few tenths to a few hundred nanometers can be formed. This review discusses the state-of-the-art of different approaches of nano-object formation by electrostatic self-assembly against the backdrop of corresponding solid materials and assemblies formed by other non-covalent interactions. In this regard, particularly promising is the facile formation of triggerable structures, i.e. size and shape switching through light, as well as the use of electrostatically assembled nano-objects for improved photocatalysis and the possible solar energy conversion in the future. Lately, this new field is eliciting an increasing amount of understanding; insights and limitations thereof are addressed in this article. Special emphasis is placed on the interconnection of molecular building block structures and the resulting nanoscale architecture via the key of thermodynamics.

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Towards supramolecular nanostructured materials: control of the self-assembly of ionic bent-core amphiphiles

Abstract: Bottom-up self-assembly: the formation of mesophases and nanostructures in solution from ionic bent-core dendrimers has been systematically studied by molecular design.

Cited by 15 publications

References 88 publications

Molecular Conformation of Bent-Core Molecules Affected by Chiral Side Chains Dictates Polymorphism and Chirality in Organic Nano- and Microfilaments

Molecular Conformation of Bent-Core Molecules Affected by Chiral Side Chains Dictates Polymorphism and Chirality in Organic Nano- and Microfilaments

Microfluidics for the rapid and controlled preparation of organic nanotubes of bent-core based dendrimers

Functional Nano-Objects by Electrostatic Self-Assembly: Structure, Switching, and Photocatalysis

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