Polymorphism in the assembly of phase-segregated block molecules: pathway control to 1D and 2D nanostructures

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Nanomaterials with highly ordered, one- or two-dimensional molecular morphologies have promising properties for adaptive materials. Here, we present the synthesis and structural characterization of dinitrohydrazone (hydz) functionalized oligodimethylsiloxanes (oDMSs) of discrete length, which form both 1- and 2D nanostructures by precisely controlling composition and temperature. The morphologies are highly ordered due to the discrete nature of the siloxane oligomers. Columnar, 1D structures are formed from the melt within a few seconds as a result of phase segregation in combination with π-π stacking of the hydrazones. By tuning the length of the siloxane, the synergy between these interactions is observed which results in a highly temperature sensitive material. Macroscopically, this gives a material that switches reversibly and fast between an ordered, solid and a disordered, liquid state at almost equal temperatures. Ordered, 2D lamellar structures are formed under thermodynamic control by cold crystallization of the hydrazones in the amorphous siloxane bulk via a slow process. We elucidate the 1- and 2D morphologies from the nanometer to molecular level by the combined use of solid state NMR and X-ray scattering. The exact packing of the hydrazone rods within the cylinders and lamellae surrounded the liquid-like siloxane matrix is clarified. These results demonstrate that controlling the assembly pathway in the bulk and with that, tuning the nanostructure dimensions and domain spacings, material properties are altered for applications in nanotechnology or thermoresponsive materials.

Originele taal-2Engels
Pagina's (van-tot)15456-15463
Aantal pagina's8
TijdschriftJournal of the American Chemical Society
Volume141
Nummer van het tijdschrift38
DOI's
StatusGepubliceerd - 25 sep 2019

Vingerafdruk

Siloxanes
Nanostructures
Polymorphism
Hydrazones
Molecules
Temperature
Tuning
Nanotechnology
Lamellar structures
Liquids
Crystallization
X ray scattering
Thermodynamics
Oligomers
Nanostructured materials
Materials properties
Switches
Nuclear magnetic resonance
X-Rays
Chemical analysis

Citeer dit

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title = "Polymorphism in the assembly of phase-segregated block molecules: pathway control to 1D and 2D nanostructures",
abstract = "Nanomaterials with highly ordered, one- or two-dimensional molecular morphologies have promising properties for adaptive materials. Here, we present the synthesis and structural characterization of dinitrohydrazone (hydz) functionalized oligodimethylsiloxanes (oDMSs) of discrete length, which form both 1- and 2D nanostructures by precisely controlling composition and temperature. The morphologies are highly ordered due to the discrete nature of the siloxane oligomers. Columnar, 1D structures are formed from the melt within a few seconds as a result of phase segregation in combination with π-π stacking of the hydrazones. By tuning the length of the siloxane, the synergy between these interactions is observed which results in a highly temperature sensitive material. Macroscopically, this gives a material that switches reversibly and fast between an ordered, solid and a disordered, liquid state at almost equal temperatures. Ordered, 2D lamellar structures are formed under thermodynamic control by cold crystallization of the hydrazones in the amorphous siloxane bulk via a slow process. We elucidate the 1- and 2D morphologies from the nanometer to molecular level by the combined use of solid state NMR and X-ray scattering. The exact packing of the hydrazone rods within the cylinders and lamellae surrounded the liquid-like siloxane matrix is clarified. These results demonstrate that controlling the assembly pathway in the bulk and with that, tuning the nanostructure dimensions and domain spacings, material properties are altered for applications in nanotechnology or thermoresponsive materials.",
author = "Lamers, {Brigitte A.G.} and Robert Graf and {de Waal}, {Bas F.M.} and Ghislaine Vantomme and Palmans, {Anja R.A.} and E.W. Meijer",
year = "2019",
month = "9",
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journal = "Journal of the American Chemical Society",
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T1 - Polymorphism in the assembly of phase-segregated block molecules

T2 - pathway control to 1D and 2D nanostructures

AU - Lamers, Brigitte A.G.

AU - Graf, Robert

AU - de Waal, Bas F.M.

AU - Vantomme, Ghislaine

AU - Palmans, Anja R.A.

AU - Meijer, E.W.

PY - 2019/9/25

Y1 - 2019/9/25

N2 - Nanomaterials with highly ordered, one- or two-dimensional molecular morphologies have promising properties for adaptive materials. Here, we present the synthesis and structural characterization of dinitrohydrazone (hydz) functionalized oligodimethylsiloxanes (oDMSs) of discrete length, which form both 1- and 2D nanostructures by precisely controlling composition and temperature. The morphologies are highly ordered due to the discrete nature of the siloxane oligomers. Columnar, 1D structures are formed from the melt within a few seconds as a result of phase segregation in combination with π-π stacking of the hydrazones. By tuning the length of the siloxane, the synergy between these interactions is observed which results in a highly temperature sensitive material. Macroscopically, this gives a material that switches reversibly and fast between an ordered, solid and a disordered, liquid state at almost equal temperatures. Ordered, 2D lamellar structures are formed under thermodynamic control by cold crystallization of the hydrazones in the amorphous siloxane bulk via a slow process. We elucidate the 1- and 2D morphologies from the nanometer to molecular level by the combined use of solid state NMR and X-ray scattering. The exact packing of the hydrazone rods within the cylinders and lamellae surrounded the liquid-like siloxane matrix is clarified. These results demonstrate that controlling the assembly pathway in the bulk and with that, tuning the nanostructure dimensions and domain spacings, material properties are altered for applications in nanotechnology or thermoresponsive materials.

AB - Nanomaterials with highly ordered, one- or two-dimensional molecular morphologies have promising properties for adaptive materials. Here, we present the synthesis and structural characterization of dinitrohydrazone (hydz) functionalized oligodimethylsiloxanes (oDMSs) of discrete length, which form both 1- and 2D nanostructures by precisely controlling composition and temperature. The morphologies are highly ordered due to the discrete nature of the siloxane oligomers. Columnar, 1D structures are formed from the melt within a few seconds as a result of phase segregation in combination with π-π stacking of the hydrazones. By tuning the length of the siloxane, the synergy between these interactions is observed which results in a highly temperature sensitive material. Macroscopically, this gives a material that switches reversibly and fast between an ordered, solid and a disordered, liquid state at almost equal temperatures. Ordered, 2D lamellar structures are formed under thermodynamic control by cold crystallization of the hydrazones in the amorphous siloxane bulk via a slow process. We elucidate the 1- and 2D morphologies from the nanometer to molecular level by the combined use of solid state NMR and X-ray scattering. The exact packing of the hydrazone rods within the cylinders and lamellae surrounded the liquid-like siloxane matrix is clarified. These results demonstrate that controlling the assembly pathway in the bulk and with that, tuning the nanostructure dimensions and domain spacings, material properties are altered for applications in nanotechnology or thermoresponsive materials.

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