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Title: Hierarchical Self-Organization of AB n Dendron-like Molecules into a Supramolecular Lattice Sequence

Abstract

To understand the hierarchical self-organization behaviors of soft materials as well as their dependence on molecular geometry, a series of ABn dendron-type giant molecules based on polyhedral oligomeric silsesquioxane (POSS) nanoparticles were designed and synthesized. The apex of these molecules is a hydrophilic POSS cage with fourteen hydroxyl groups (denoted DPOSS). At its periphery, there are different numbers (n = 1–8) of hydrophobic POSS cages with seven isobutyl groups (denoted BPOSS), connected to the apical DPOSS via flexible dendron type linker(s). With varying the BPOSS number from one to seven, a supramolecular lattice formation sequence ranging from lamella (DPOSS-BPOSS), double gyroid (space group of Ia3d, DPOSS-BPOSS2), hexagonal cylinder (space group of P6mm, DPOSS-BPOSS3), Frank-Kasper A15 (space group of Pm3n, DPOSS-BPOSS4, DPOSS-BPOSS5, and DPOSS-BPOSS6), to Frank-Kasper sigma (space group of P42/mnm, DPOSS-BPOSS7) phases can be observed. The nanostructure formations in this series of ABn dendron-type giant molecules are mainly directed by the macromolecular geometric shapes. Furthermore, within each spherical motif, the soft spherical core is consisted of hydrophilic DPOSS cages with flexible linkages, while the hydrophobic BPOSS cages form the relative rigid shell and contact with neighbors to provide decreased interfaces among the spherical motifs for constructing final polyhedral motifs inmore » these Frank-Kasper lattices. This study provides the design principle of macromolecules with specific geometric shapes and functional groups to achieve anticipated structures and macroscopic properties.« less

Authors:
 [1];  [1]; ORCiD logo [2];  [3];  [1];  [1];  [1];  [1];  [1];  [1];  [3];  [1];  [4]; ORCiD logo [1];  [5]; ORCiD logo [1]
  1. Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron, Akron, Ohio 44325-3909, United States
  2. College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610065, China
  3. RIKEN CLST-JEOL Collaboration Center, RIKEN, Yokohama 230-0045, Japan; JEOL RESONANCE Inc., Tokyo 196-8558, Japan
  4. South China Advanced Institute for Soft Matter Science and Technology, South China University of Technology, Guangzhou 510640, China
  5. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois, 60439, United States
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1389624
DOE Contract Number:
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Central Science; Journal Volume: 3; Journal Issue: 8
Country of Publication:
United States
Language:
English

Citation Formats

Feng, Xueyan, Zhang, Ruimeng, Li, Yiwen, Hong, You-lee, Guo, Dong, Lang, Kening, Wu, Kuan-Yi, Huang, Mingjun, Mao, Jialin, Wesdemiotis, Chrys, Nishiyama, Yusuke, Zhang, Wei, Zhang, Wei, Miyoshi, Toshikazu, Li, Tao, and Cheng, Stephen Z. D.. Hierarchical Self-Organization of AB n Dendron-like Molecules into a Supramolecular Lattice Sequence. United States: N. p., 2017. Web. doi:10.1021/acscentsci.7b00188.
Feng, Xueyan, Zhang, Ruimeng, Li, Yiwen, Hong, You-lee, Guo, Dong, Lang, Kening, Wu, Kuan-Yi, Huang, Mingjun, Mao, Jialin, Wesdemiotis, Chrys, Nishiyama, Yusuke, Zhang, Wei, Zhang, Wei, Miyoshi, Toshikazu, Li, Tao, & Cheng, Stephen Z. D.. Hierarchical Self-Organization of AB n Dendron-like Molecules into a Supramolecular Lattice Sequence. United States. doi:10.1021/acscentsci.7b00188.
Feng, Xueyan, Zhang, Ruimeng, Li, Yiwen, Hong, You-lee, Guo, Dong, Lang, Kening, Wu, Kuan-Yi, Huang, Mingjun, Mao, Jialin, Wesdemiotis, Chrys, Nishiyama, Yusuke, Zhang, Wei, Zhang, Wei, Miyoshi, Toshikazu, Li, Tao, and Cheng, Stephen Z. D.. 2017. "Hierarchical Self-Organization of AB n Dendron-like Molecules into a Supramolecular Lattice Sequence". United States. doi:10.1021/acscentsci.7b00188.
@article{osti_1389624,
title = {Hierarchical Self-Organization of AB n Dendron-like Molecules into a Supramolecular Lattice Sequence},
author = {Feng, Xueyan and Zhang, Ruimeng and Li, Yiwen and Hong, You-lee and Guo, Dong and Lang, Kening and Wu, Kuan-Yi and Huang, Mingjun and Mao, Jialin and Wesdemiotis, Chrys and Nishiyama, Yusuke and Zhang, Wei and Zhang, Wei and Miyoshi, Toshikazu and Li, Tao and Cheng, Stephen Z. D.},
abstractNote = {To understand the hierarchical self-organization behaviors of soft materials as well as their dependence on molecular geometry, a series of ABn dendron-type giant molecules based on polyhedral oligomeric silsesquioxane (POSS) nanoparticles were designed and synthesized. The apex of these molecules is a hydrophilic POSS cage with fourteen hydroxyl groups (denoted DPOSS). At its periphery, there are different numbers (n = 1–8) of hydrophobic POSS cages with seven isobutyl groups (denoted BPOSS), connected to the apical DPOSS via flexible dendron type linker(s). With varying the BPOSS number from one to seven, a supramolecular lattice formation sequence ranging from lamella (DPOSS-BPOSS), double gyroid (space group of Ia3d, DPOSS-BPOSS2), hexagonal cylinder (space group of P6mm, DPOSS-BPOSS3), Frank-Kasper A15 (space group of Pm3n, DPOSS-BPOSS4, DPOSS-BPOSS5, and DPOSS-BPOSS6), to Frank-Kasper sigma (space group of P42/mnm, DPOSS-BPOSS7) phases can be observed. The nanostructure formations in this series of ABn dendron-type giant molecules are mainly directed by the macromolecular geometric shapes. Furthermore, within each spherical motif, the soft spherical core is consisted of hydrophilic DPOSS cages with flexible linkages, while the hydrophobic BPOSS cages form the relative rigid shell and contact with neighbors to provide decreased interfaces among the spherical motifs for constructing final polyhedral motifs in these Frank-Kasper lattices. This study provides the design principle of macromolecules with specific geometric shapes and functional groups to achieve anticipated structures and macroscopic properties.},
doi = {10.1021/acscentsci.7b00188},
journal = {ACS Central Science},
number = 8,
volume = 3,
place = {United States},
year = 2017,
month = 8
}
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