Controlling the Spatial Organization of Liquid Crystalline Nanoparticles by Composition of the Organic Grafting Layer

Wójcik, Michał; Olesińska, Magdalena; Sawczyk, Michał; Mieczkowski, Józef; Górecka, Ewa

doi:10.1002/chem.201406262

Cited by 10 publications

(15 citation statements)

References 41 publications

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“…The presenceo f nanoparticles does not affect the thermals tability of the polymers. The gold chemistry in hybrid elastomers determined by XPS scans was very similar to that observed previously for an anoparticle system [20] (inset in Figure S15 of the Supporting Information), and as expected there were no changes in the bonding between the L2 ligand and metal surface induced by the polymerization procedure. The composition of polymer samples was also studied by X-ray photoelectron spectroscopy (XPS;s ee the Supporting Information, Figures S13-S15).…”

Section: Materials Propertiessupporting

confidence: 84%

Liquid‐Crystalline Elastomers with Gold Nanoparticle Cross‐Linkers

Wójcik

Wróbel

Jańczuk

et al. 2017

Chemistry A European J

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Embedding nanoparticles in a responsive polymer matrix is a formidable way to fabricate hybrid materials with predesigned properties and prospective applications in actuators, mechanically tunable optical elements, and electroclinic films. However, achieving chemical compatibility between nanoparticles and organic matter is not trivial and often results in disordered structures. Herein, it is shown that using nanoparticles as exclusive cross-linkers in the preparation of liquid-crystalline polymers can yield long-range-ordered liquid-crystalline elastomers with high loadings of well-dispersed nanoparticles, as confirmed by small-angle XRD measurements. Moreover, the strategy of incorporating NPs as cross-linking units does not result in disruption of mechanical properties of the polymer, and this phenomenon was explained by the means of all-atom molecular dynamics simulations. Such materials can exhibit switchable behavior under thermal stimulus with stability spanning over multiple heating/cooling cycles. The presented strategy has proven to be a promising approach for the preparation of new types of hybrid liquid-crystalline elastomers that can be of value for future photonic applications.

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Section: Materials Propertiessupporting

confidence: 84%

Liquid‐Crystalline Elastomers with Gold Nanoparticle Cross‐Linkers

Wójcik

Wróbel

Jańczuk

et al. 2017

Chemistry A European J

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“…Presented promesogenic ligand (L M ) is a synthetic modification of previously studied organic compounds which allow nanoparticles to organize into various types of lamellar and 3D phases, but has only been successful with small diameter particles . In the current study a derivative of undecanoic acid and decano‐1,10‐diol (Scheme S1, Supporting Information) was used as a spacer—a flexible part of ligand that anchors a rigid molecular core to the nanoparticle surface.…”

Section: Resultsmentioning

confidence: 99%

Gold Nanoparticles Thin Films with Thermo‐ and Photoresponsive Plasmonic Properties Realized with Liquid‐Crystalline Ligands

Tomczyk

Promiński

Bagiński

et al. 2019

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Robust synthesis of large‐scale self‐assembled nanostructures with long‐range organization and a prominent response to external stimuli is critical to their application in functional plasmonics. Here, the first example of a material made of liquid crystalline nanoparticles which exhibits UV‐light responsive surface plasmon resonance in a condensed state is presented. To obtain the material, metal cores are grafted with two types of organic ligands. A promesogenic derivative softens the system and induces rich liquid crystal phase polymorphism. Second, an azobenzene derivative endows nanoparticles with photoresponsive properties. It is shown that nanoparticles covered with a mixture of these ligands assemble into long‐range ordered structures which exhibit a novel dual‐responsivity. The structure and plasmonic properties of the assemblies can be controlled by a change in temperature as well as by UV‐light irradiation. These results present an efficient way to obtain bulk quantities of self‐assembled nanostructured materials with stability that is unattainable by alternative methods such as matrix‐assisted or DNA‐mediated organization.

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“…Notably, several design parameters allowing tailoring properties of LC NPs have been identified. In majority, they relate to the (pro)mesogenic ligands: geometry of the LC-molecule [ 46 , 47 , 48 , 49 ], its volume [ 50 ], LC ligand alkyl spacer length [ 46 , 47 ], as well as density of LC-ligands grafting [ 51 ]. Much less effort was put to determining the role of alkyl ligands for which only the influence of length was examined and shown to determine the symmetry of the assemblies (by influencing overall shape of the organic coating layer) [ 47 , 52 ], as well as to influence the thermal response of the material (by influencing spatial rearrangement of LC ligands) [ 46 ].…”

Section: Introductionmentioning

confidence: 99%

Modifying Thermal Switchability of Liquid Crystalline Nanoparticles by Alkyl Ligands Variation

et al. 2018

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By coating plasmonic nanoparticles (NPs) with thermally responsive liquid crystals (LCs) it is possible to prepare reversibly reconfigurable plasmonic nanomaterials with prospective applications in optoelectronic devices. However, simple and versatile methods to precisely tailor properties of liquid-crystalline nanoparticles (LC NPs) are still required. Here, we report a new method for tuning structural properties of assemblies of nanoparticles grafted with a mixture of promesogenic and alkyl thiols, by varying design of the latter. As a model system, we used Ag and Au nanoparticles that were coated with three-ring promesogenic molecules and dodecanethiol ligand. These LC NPs self-assemble into switchable lamellar (Ag NPs) or tetragonal (Au NPs) aggregates, as determined with small angle X-ray diffraction and transmission electron microscopy. Reconfigurable assemblies of Au NPs with different unit cell symmetry (orthorombic) are formed if hexadecanethiol and 1H,1H,2H,2H-perfluorodecanethiol were used in the place of dodecanethiol; in the case of Ag NPs the use of 11-hydroxyundecanethiol promotes formation of a lamellar structure as in the reference system, although with substantially broader range of thermal stability (140 vs. 90 °C). Our results underline the importance of alkyl ligand functionalities in determining structural properties of liquid-crystalline nanoparticles, and, more generally, broaden the scope of synthetic tools available for tailoring properties of reversibly reconfigurable plasmonic nanomaterials.

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Controlling the Spatial Organization of Liquid Crystalline Nanoparticles by Composition of the Organic Grafting Layer

Cited by 10 publications

References 41 publications

Liquid‐Crystalline Elastomers with Gold Nanoparticle Cross‐Linkers

Liquid‐Crystalline Elastomers with Gold Nanoparticle Cross‐Linkers

Gold Nanoparticles Thin Films with Thermo‐ and Photoresponsive Plasmonic Properties Realized with Liquid‐Crystalline Ligands

Modifying Thermal Switchability of Liquid Crystalline Nanoparticles by Alkyl Ligands Variation

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