Mesoscale Frank-Kasper Crystal Structures from Dendron Assembly by Controlling Core Apex Interactions

Taesuk Jun; Hyunjun Park; Seungbae Jeon; Seungyun Jo; Hyungju Ahn; Woo Dong Jang; Byeongdu Lee; Du Yeol Ryu

doi:10.1021/jacs.1c07313

Mesoscale Frank-Kasper Crystal Structures from Dendron Assembly by Controlling Core Apex Interactions

Taesuk Jun, Hyunjun Park, Seungbae Jeon, Seungyun Jo, Hyungju Ahn, Woo Dong Jang, Byeongdu Lee, Du Yeol Ryu

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

Abstract

Single-component polymeric materials open up a great potential for self-assembly into mesoscale complex crystal structures that are known as Frank-Kasper (FK) phases. Predicting the packing structures of the soft-matter spheres, however, remains a challenge even when the molecular design is precisely known. Here, we investigate the role of the molecules' enthalpic interaction in determining the low-symmetry crystal structures. To this end, we synthesize architecturally asymmetric dendrons by varying their apex functionalities and examine the packing structures of the second-generation (G2) dendritic wedges. Our work shows that weakening the hydrogen bonding of the dendron apex makes the particles softer and smaller, and leads to the formation of various FK structures at lower temperatures, including the new observation of a FK C14 phase in the cone-shaped dendron systems. As a consequence of the free energy balance between the particle's interfacial tension and the chain's stretching, various packing structures are mainly tuned by designing the hydrogen bonding interaction.

Original language	English
Pages (from-to)	17548-17556
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	143
Issue number	42
DOIs	https://doi.org/10.1021/jacs.1c07313
Publication status	Published - 2021 Oct 27

Bibliographical note

Funding Information:
SAXS measurements were performed at Pohang Accelerator Laboratory (Korea) (4C and 9A beamlines) and Advanced Photon Source in the Argonne National Laboratory (U.S.) (12-ID-B beamline). The use of the APS is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract DE-AC0206CH11357. This work was supported by Samsung Research Funding Center for Samsung Electronics (SRFC-MA1801-04), Korea. We also acknowledge the NRF Grants 2021R1A2C2006588 and 2020R1A2C3004520 funded by the Ministry of Science, ICT & Future Planning (MSIP), Korea.

Publisher Copyright:
© 2021 American Chemical Society.

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.1c07313

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abstract = "Single-component polymeric materials open up a great potential for self-assembly into mesoscale complex crystal structures that are known as Frank-Kasper (FK) phases. Predicting the packing structures of the soft-matter spheres, however, remains a challenge even when the molecular design is precisely known. Here, we investigate the role of the molecules' enthalpic interaction in determining the low-symmetry crystal structures. To this end, we synthesize architecturally asymmetric dendrons by varying their apex functionalities and examine the packing structures of the second-generation (G2) dendritic wedges. Our work shows that weakening the hydrogen bonding of the dendron apex makes the particles softer and smaller, and leads to the formation of various FK structures at lower temperatures, including the new observation of a FK C14 phase in the cone-shaped dendron systems. As a consequence of the free energy balance between the particle's interfacial tension and the chain's stretching, various packing structures are mainly tuned by designing the hydrogen bonding interaction.",

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note = "Funding Information: SAXS measurements were performed at Pohang Accelerator Laboratory (Korea) (4C and 9A beamlines) and Advanced Photon Source in the Argonne National Laboratory (U.S.) (12-ID-B beamline). The use of the APS is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract DE-AC0206CH11357. This work was supported by Samsung Research Funding Center for Samsung Electronics (SRFC-MA1801-04), Korea. We also acknowledge the NRF Grants 2021R1A2C2006588 and 2020R1A2C3004520 funded by the Ministry of Science, ICT & Future Planning (MSIP), Korea. Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

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Mesoscale Frank-Kasper Crystal Structures from Dendron Assembly by Controlling Core Apex Interactions

Abstract

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