Mesoscale Frank–Kasper Crystal Structures from Dendron Assembly by Controlling Core Apex Interactions
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.
- Authors:
-
[1];
[3];
[1]
- Yonsei Univ., Seoul (South Korea)
- Pohang Accelerator Lab. (PAL) (South Korea). Industry Technology Convergence Center
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Samsung Electronics; National Research Foundation of Korea (NRF)
- OSTI Identifier:
- 1834774
- Grant/Contract Number:
- AC02-06CH11357; 2021R1A2C2006588; 2020R1A2-C3004520; SRFC-MA1801-04
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 143; Journal Issue: 42; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Jun, Taesuk, Park, Hyunjun, Jeon, Seungbae, Jo, Seungyun, Ahn, Hyungju, Jang, Woo-Dong, Lee, Byeongdu, and Ryu, Du Yeol. Mesoscale Frank–Kasper Crystal Structures from Dendron Assembly by Controlling Core Apex Interactions. United States: N. p., 2021.
Web. doi:10.1021/jacs.1c07313.
Jun, Taesuk, Park, Hyunjun, Jeon, Seungbae, Jo, Seungyun, Ahn, Hyungju, Jang, Woo-Dong, Lee, Byeongdu, & Ryu, Du Yeol. Mesoscale Frank–Kasper Crystal Structures from Dendron Assembly by Controlling Core Apex Interactions. United States. https://doi.org/10.1021/jacs.1c07313
Jun, Taesuk, Park, Hyunjun, Jeon, Seungbae, Jo, Seungyun, Ahn, Hyungju, Jang, Woo-Dong, Lee, Byeongdu, and Ryu, Du Yeol. Fri .
"Mesoscale Frank–Kasper Crystal Structures from Dendron Assembly by Controlling Core Apex Interactions". United States. https://doi.org/10.1021/jacs.1c07313. https://www.osti.gov/servlets/purl/1834774.
@article{osti_1834774,
title = {Mesoscale Frank–Kasper Crystal Structures from Dendron Assembly by Controlling Core Apex Interactions},
author = {Jun, Taesuk and Park, Hyunjun and Jeon, Seungbae and Jo, Seungyun and Ahn, Hyungju and Jang, Woo-Dong and Lee, Byeongdu and Ryu, Du Yeol},
abstractNote = {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.},
doi = {10.1021/jacs.1c07313},
journal = {Journal of the American Chemical Society},
number = 42,
volume = 143,
place = {United States},
year = {Fri Oct 15 00:00:00 EDT 2021},
month = {Fri Oct 15 00:00:00 EDT 2021}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Conformational Asymmetry and Quasicrystal Approximants in Linear Diblock Copolymers
journal, May 2017
- Schulze, Morgan W.; Lewis, Ronald M.; Lettow, James H.
- Physical Review Letters, Vol. 118, Issue 20
An Exceptionally Stable and Scalable Sugar–Polyolefin Frank–Kasper A15 Phase
journal, January 2020
- Lachmayr, Kätchen K.; Wentz, Charlotte M.; Sita, Lawrence R.
- Angewandte Chemie International Edition, Vol. 59, Issue 4
Exploring and Expanding the Structural Diversity of Self-Assembling Dendrons through Combinations of AB, Constitutional Isomeric AB2, and AB3 Biphenyl-4-Methyl Ether Building Blocks
journal, August 2006
- Percec, Virgil; Holerca, Marian N.; Nummelin, Sami
- Chemistry - A European Journal, Vol. 12, Issue 24
Self-Assembly of Dendritic Crowns into Chiral Supramolecular Spheres
journal, January 2009
- Percec, Virgil; Imam, Mohammad R.; Peterca, Mihai
- Journal of the American Chemical Society, Vol. 131, Issue 3
Giant Supramolecular Liquid Crystal Lattice
journal, February 2003
- Ungar, G.
- Science, Vol. 299, Issue 5610
Self-Assembly of Dendronized Triphenylenes into Helical Pyramidal Columns and Chiral Spheres
journal, June 2009
- Percec, Virgil; Imam, Mohammad R.; Peterca, Mihai
- Journal of the American Chemical Society, Vol. 131, Issue 22
Concerning the relative numbers of atomic coordination types in tetrahedrally close packed metal structures
journal, February 1986
- Shoemaker, D. P.; Shoemaker, C. B.
- Acta Crystallographica Section B Structural Science, Vol. 42, Issue 1
Stable Frank–Kasper phases of self-assembled, soft matter spheres
journal, September 2018
- Reddy, Abhiram; Buckley, Michael B.; Arora, Akash
- Proceedings of the National Academy of Sciences, Vol. 115, Issue 41
Dendronized Poly(2-oxazoline) Displays within only Five Monomer Repeat Units Liquid Quasicrystal, A15 and σ Frank–Kasper Phases
journal, November 2018
- Holerca, Marian N.; Sahoo, Dipankar; Partridge, Benjamin E.
- Journal of the American Chemical Society, Vol. 140, Issue 49
Hierarchical Self-Organization of AB n Dendron-like Molecules into a Supramolecular Lattice Sequence
journal, August 2017
- Feng, Xueyan; Zhang, Ruimeng; Li, Yiwen
- ACS Central Science, Vol. 3, Issue 8
Predicting the Structure of Supramolecular Dendrimers via the Analysis of Libraries of AB 3 and Constitutional Isomeric AB 2 Biphenylpropyl Ether Self-Assembling Dendrons
journal, December 2009
- Rosen, Brad M.; Wilson, Daniela A.; Wilson, Christopher J.
- Journal of the American Chemical Society, Vol. 131, Issue 47
Preparation of polymers with controlled molecular architecture. A new convergent approach to dendritic macromolecules
journal, October 1990
- Hawker, Craig J.; Frechet, Jean M. J.
- Journal of the American Chemical Society, Vol. 112, Issue 21
Laves Phases Formed in the Binary Blend of AB 4 Miktoarm Star Copolymer and A-Homopolymer
journal, February 2019
- Zhao, Mingtian; Li, Weihua
- Macromolecules, Vol. 52, Issue 4
Supramolecular dendritic liquid quasicrystals
journal, March 2004
- Zeng, Xiangbing; Ungar, Goran; Liu, Yongsong
- Nature, Vol. 428, Issue 6979
Heat-Shrinking Spherical and Columnar Supramolecular Dendrimers: Their Interconversion and Dependence of Their Shape on Molecular Taper Angle
journal, April 2000
- Ungar, Goran; Percec, Virgil; Holerca, Marian N.
- Chemistry - A European Journal, Vol. 6, Issue 7
From structure to function via complex supramolecular dendrimer systems
journal, January 2015
- Sun, Hao-Jan; Zhang, Shaodong; Percec, Virgil
- Chemical Society Reviews, Vol. 44, Issue 12
Design and Structural Analysis of the First Spherical Monodendron Self-Organizable in a Cubic Lattice
journal, May 2000
- Percec, Virgil; Cho, Wook-Dong; Möller, Martin
- Journal of the American Chemical Society, Vol. 122, Issue 17
Direct AFM observation of individual micelles, tile decorations and tiling rules of a dodecagonal liquid quasicrystal
journal, September 2017
- Zhang, Ruibin; Zeng, Xiangbing; Ungar, Goran
- Journal of Physics: Condensed Matter, Vol. 29, Issue 41
Stacking entropy of hard-sphere crystals
journal, April 1999
- Mau, Siun-Chuon; Huse, David A.
- Physical Review E, Vol. 59, Issue 4
Maximizing Entropy by Minimizing Area: Towards a New Principle of Self-Organization
journal, October 2001
- Ziherl, P.; Kamien, Randall D.
- The Journal of Physical Chemistry B, Vol. 105, Issue 42
Discovery of a Frank-Kasper Phase in Sphere-Forming Block Copolymer Melts
journal, October 2010
- Lee, S.; Bluemle, M. J.; Bates, F. S.
- Science, Vol. 330, Issue 6002
Designing Libraries of First Generation AB 3 and AB 2 Self-Assembling Dendrons via the Primary Structure Generated from Combinations of (AB) y −AB 3 and (AB) y −AB 2 Building Blocks
journal, May 2004
- Percec, Virgil; Mitchell, Catherine M.; Cho, Wook-Dong
- Journal of the American Chemical Society, Vol. 126, Issue 19
Transition Kinetics of Self-Assembled Supramolecular Dodecagonal Quasicrystal and Frank–Kasper σ Phases in AB n Dendron-Like Giant Molecules
journal, June 2019
- Feng, Xueyan; Liu, Gengxin; Guo, Dong
- ACS Macro Letters, Vol. 8, Issue 7
Complex alloy structures regarded as sphere packings. I. Definitions and basic principles
journal, March 1958
- Frank, F. C.; Kasper, J. S.
- Acta Crystallographica, Vol. 11, Issue 3
Coassembly of a Hexagonal Columnar Liquid Crystalline Superlattice from Polymer(s) Coated with a Three-Cylindrical Bundle Supramolecular Dendrimer
journal, March 1999
- Percec, Virgil; Ahn, Cheol-H.; Bera, Tushar K.
- Chemistry - A European Journal, Vol. 5, Issue 3
Identification of a Frank–Kasper Z phase from shape amphiphile self-assembly
journal, September 2019
- Su, Zebin; Hsu, Chih-Hao; Gong, Zihao
- Nature Chemistry, Vol. 11, Issue 10
σ Phase Formed in Conformationally Asymmetric AB-Type Block Copolymers
journal, August 2014
- Xie, Nan; Li, Weihua; Qiu, Feng
- ACS Macro Letters, Vol. 3, Issue 9
Supramolecular spheres assembled from covalent and supramolecular dendritic crowns dictate the supramolecular orientational memory effect mediated by Frank–Kasper phases
journal, March 2020
- Huang, Ning; Imam, Mohammad R.; Sienkowska, Monika J.
- Giant, Vol. 1
Sphericity and symmetry breaking in the formation of Frank–Kasper phases from one component materials
journal, November 2014
- Lee, Sangwoo; Leighton, Chris; Bates, Frank S.
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 50
Ordered micellar and inverse micellar lyotropic phases
journal, July 2010
- Shearman, G. C.; Tyler, A. I. I.; Brooks, N. J.
- Liquid Crystals, Vol. 37, Issue 6-7
Entropy difference between crystal phases
journal, July 1997
- Bolhuis, P. G.; Frenkel, D.; Mau, Siun-Choun
- Nature, Vol. 388, Issue 6639
Synthesis and Retrostructural Analysis of Libraries of AB 3 and Constitutional Isomeric AB 2 Phenylpropyl Ether-Based Supramolecular Dendrimers
journal, March 2006
- Percec, Virgil; Peterca, Mihai; Sienkowska, Monika J.
- Journal of the American Chemical Society, Vol. 128, Issue 10
Complex alloy structures regarded as sphere packings. II. Analysis and classification of representative structures
journal, July 1959
- Frank, F. C.; Kasper, J. S.
- Acta Crystallographica, Vol. 12, Issue 7
From Molecular Flat Tapers, Discs, and Cones to Supramolecular Cylinders and Spheres using Fréchet-Type Monodendrons Modified on their Periphery
journal, May 2000
- Percec, Virgil; Cho, Wook-Dong; Ungar, Goran
- Angewandte Chemie International Edition, Vol. 39, Issue 9
Self-organisation of rhombitruncated cuboctahedral hexagonal columns from an amphiphilic Janus dendrimer
journal, March 2021
- Huang, Ning; Xiao, Qi; Peterca, Mihai
- Molecular Physics, Vol. 119, Issue 19-20
Exploring and Expanding the Three-Dimensional Structural Diversity of Supramolecular Dendrimers with the Aid of Libraries of Alkali Metals of Their AB3 Minidendritic Carboxylates
journal, March 2002
- Percec, Virgil; Holerca, Marian N.; Uchida, Satoshi
- Chemistry - A European Journal, Vol. 8, Issue 5
Rational Design of the First Spherical Supramolecular Dendrimers Self-Organized in a Novel Thermotropic Cubic Liquid-Crystalline Phase and the Determination of Their Shape by X-ray Analysis
journal, February 1997
- Balagurusamy, V. S. K.; Ungar, G.; Percec, V.
- Journal of the American Chemical Society, Vol. 119, Issue 7
Thermal processing of diblock copolymer melts mimics metallurgy
journal, May 2017
- Kim, Kyungtae; Schulze, Morgan W.; Arora, Akash
- Science, Vol. 356, Issue 6337
Liquid crystalline polymers containing mesogenic units based on half-disc and rod-like moieties. I. Synthesis and characterization of 4-(11-undecan-1-yloxy)-4′-[3,4,5-tri(p-n-dodecan-1-yloxybenzyloxy)benzoate]biphenyl side groups
journal, March 1991
- Percec, V.; Heck, J.
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 29, Issue 4
Effect of Temperature on the Supramolecular Tubular Structure in Oriented Fibers of a Poly(methacrylate) with Tapered Side Groups
journal, February 1995
- Kwon, Yong Ku; Chvalun, Sergei N.; Blackwell, John
- Macromolecules, Vol. 28, Issue 5
Recasting Metal Alloy Phases with Block Copolymers
journal, October 2010
- Peterca, M.; Percec, V.
- Science, Vol. 330, Issue 6002
Selective assemblies of giant tetrahedra via precisely controlled positional interactions
journal, April 2015
- Huang, M.; Hsu, C. -H.; Wang, J.
- Science, Vol. 348, Issue 6233
Increasing the Diameter of Cylindrical and Spherical Supramolecular Dendrimers by Decreasing the Solid Angle of Their Monodendrons via Periphery Functionalization
journal, October 2000
- Percec, Virgil; Cho, Wook-Dong; Ungar, Goran
- Journal of the American Chemical Society, Vol. 122, Issue 42
Direct Visualization of Individual Cylindrical and Spherical Supramolecular Dendrimers
journal, October 1997
- Hudson, S. D.
- Science, Vol. 278, Issue 5337
Deconstruction as a Strategy for the Design of Libraries of Self-Assembling Dendrons
journal, August 2010
- Rosen, Brad M.; Peterca, Mihai; Huang, Chenghong
- Angewandte Chemie International Edition, Vol. 49, Issue 39
Expanding the Structural Diversity of Self-Assembling Dendrons and Supramolecular Dendrimers via Complex Building Blocks
journal, August 2007
- Percec, Virgil; Won, Betty C.; Peterca, Mihai
- Journal of the American Chemical Society, Vol. 129, Issue 36
Structural Analysis of Cylindrical and Spherical Supramolecular Dendrimers Quantifies the Concept of Monodendron Shape Control by Generation Number
journal, November 1998
- Percec, V.; Cho, W. -D.; Mosier, P. E.
- Journal of the American Chemical Society, Vol. 120, Issue 43
Synthesis and Structural Analysis of Two Constitutional Isomeric Libraries of AB 2 -Based Monodendrons and Supramolecular Dendrimers
journal, February 2001
- Percec, Virgil; Cho, Wook-Dong; Ungar, Goran
- Journal of the American Chemical Society, Vol. 123, Issue 7
Rational Route Toward the Frank–Kasper Z Phase: Effect of Precise Geometrical Tuning on the Supramolecular Assembly of Giant Shape Amphiphiles
journal, August 2021
- Huang, Jiahao; Zhang, Ruimeng; Wang, Yicong
- Macromolecules, Vol. 54, Issue 17
Frank–Kasper Phases Identified in PDMS‐ b ‐PTFEA Copolymers with High Conformational Asymmetry
journal, July 2019
- Jeon, Seungbae; Jun, Taesuk; Jo, Seongjun
- Macromolecular Rapid Communications, Vol. 40, Issue 19
Efficiency of Various Lattices from Hard Ball to Soft Ball: Theoretical Study of Thermodynamic Properties of Dendrimer Liquid Crystal from Atomistic Simulation
journal, February 2004
- Li, Youyong; Lin, Shiang-Tai; Goddard, William A.
- Journal of the American Chemical Society, Vol. 126, Issue 6
Frank–Kasper, quasicrystalline and related phases in liquid crystals
journal, January 2005
- Ungar, Goran; Zeng, Xiangbing
- Soft Matter, Vol. 1, Issue 2
End-Group Chemistry and Junction Chemistry in Polymer Science: Past, Present, and Future
journal, January 2020
- Kim, Jihoon; Jung, Ha Young; Park, Moon Jeong
- Macromolecules, Vol. 53, Issue 3
Controlling polymer shape through the self-assembly of dendritic side-groups
journal, January 1998
- Percec, V.; Ahn, C.-H.; Ungar, G.
- Nature, Vol. 391, Issue 6663, p. 161-164
Self-Assembly of Colloidal Nanocrystals: From Intricate Structures to Functional Materials
journal, August 2016
- Boles, Michael A.; Engel, Michael; Talapin, Dmitri V.
- Chemical Reviews, Vol. 116, Issue 18
Dendron-Mediated Self-Assembly, Disassembly, and Self-Organization of Complex Systems
journal, November 2009
- Rosen, Brad M.; Wilson, Christopher J.; Wilson, Daniela A.
- Chemical Reviews, Vol. 109, Issue 11
Low-symmetry sphere packings of simple surfactant micelles induced by ionic sphericity
journal, April 2017
- Kim, Sung A.; Jeong, Kyeong-Jun; Yethiraj, Arun
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 16
Dodecagonal quasicrystals of oil-swollen ionic surfactant micelles
journal, July 2021
- Jayaraman, Ashish; Baez-Cotto, Carlos M.; Mann, Tyler J.
- Proceedings of the National Academy of Sciences, Vol. 118, Issue 31