Conformational Preferences and the Phase Stability of Fullerene Hexa‐adducts

Wu, Szu-Hsien; Hong, Chen Yang; Wu, Kuan Yi; Lan, Shih Ting; Hsieh, Chou Ting; Chen, Hsin Lung; Wang, Chien‐Lung

doi:10.1002/asia.201600543

Cited by 6 publications

(4 citation statements)

References 41 publications

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“…In supramolecular chemistry, it is important to let the structural factors imbedded at the molecular level be transferred up to the higher hierarchical levels. To connect the shapeshifting between the molecular and supramolecular levels, herein, we incorporated the conformational flexibility of star molecules , into the design of giant molecules to develop a shapeshifting molecule that accesses the Ostwald’s stages of nucleation. The design principle was inspired first by Saez and Goodby, who have demonstrated that the gross shapes of star-like molecules can be adjusted by chemically modifying the density and attachment orientation of the peripheral mesogenic groups .…”

Section: Introductionmentioning

confidence: 99%

Connecting Molecular and Supramolecular Shapeshifting by the Ostwald’s Nucleation Stages of a Star Giant Molecule

Hsu

Cheng

et al. 2022

J. Am. Chem. Soc.

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The shapeshifting behavior for synthetic matters was found at either the molecular or supramolecular level, but the connection between shapeshifting at the two hierarchical levels remains missing. In this study, an 8-arm star giant molecule, NPOSS, was synthesized to connect the molecular and supramolecular shapeshifting. Controlling the conditions of bulk self-assembly allowed us to bring NPOSS into three different Ostwald’s stages of nucleation. The high conformational flexibility of NPOSS facilitates molecular shapeshifting and allows NPOSS to take the discotic, rod-like and star-like geometries in different Ostwald’s stages. Simultaneous changes in the supramolecular scaffolds were observed as the discotic, rod-like and star-like NPOSS molecules self-assembled into the supramolecular scaffolds of 1D columns, 2D lamellae, and 3D networks, respectively. These changes in the hierarchical structures also affect the CO2 affinity of NPOSS. Therefore, the connection between the molecular/supramolecular shapeshifting and the structure-driven property changes of NPOSS were established by taking advantage of the high conformational freedom of the 8-arm star giant molecule and its diverse self-assembly pathways leading to the different Ostwald’s stages.

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Section: Introductionmentioning

confidence: 99%

Connecting Molecular and Supramolecular Shapeshifting by the Ostwald’s Nucleation Stages of a Star Giant Molecule

Hsu

Cheng

et al. 2022

J. Am. Chem. Soc.

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“…In multicomponent systems, the molar fraction of the constituent components is an essential factor that governs physical properties, physical transitions, and self-assembly of a system . Changes in the molar fractions of the constituent components alter the stabilities of the physical states of a system and result in changes in the self-assembly morphologies. − For example, manipulating the molar fraction of the constituent components in block copolymers and giant molecules , has enabled the system to create supramolecular architectures, including 1D nanorods, 2D nanosheets, and 3D interpenetrating networks. − …”

Section: Introductionmentioning

confidence: 99%

Composition-Driven Structural Modulation and Guest-Induced Nanotemplate Effects of the Host–Guest Complexes Made by a Unimolecular Q-Clip

Yang

Lin

et al. 2021

Macromolecules

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The composition of a self-assembly system has long been an essential factor that governs the resulting supramolecular structures. Nevertheless, due to the rigorous demands of structural compatibility in host–guest chemistry, the molar ratio of host–guest mixtures has not been applied as a significant factor in modulating the supramolecular structures of host–guest complexes. In this study, via using a novel unimolecular quaternary clip (Q-clip) as the host molecule and pyrene as the guest molecule and a nanotemplating reagent, we discovered that the changes in the molar ratios of the Q-clip:pyrene mixtures resulted in the structural modulation of the host–guest complexes. Supramolecular lamellae made by the 1:4 Q-clip:pyrene mixture and a hexagonal columnar phase (Colh) made by the 1:8 Q-clip:pyrene mixture were identified by the 1D powder and 2D fiber WAXS characterizations. Time-resolved synchrotron X-ray characterization and thermal analysis further showed that removing the easily sublimed guest molecules (pyrene) via thermal annealing simply hollowed out the supramolecular structures without damaging the supramolecular scaffolds made by the Q-clips. Pyrene is thus a nanotemplating reagent that can be used to create the hollowed-out 2D lamellar and 1D cylindrical scaffolds of Q-clips. The study thus gave a novel example of a host–guest mixture that is able to carry out composition-driven structural modulation and guest-induced nanotemplates. The finding broadens the horizon of host–guest chemistry and may inspire more nanoinnovation.

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“…In addition to their use as nano‐building blocks, MNPs such as C 60 and POSS have also been applied as the core units of dendrimers. By attaching peripheral functional units, as shown in Figure , functional materials including amphiphilic MNPs, photoactive MNPs, electroactive MNPs, and bioactive MNPs have been synthesized.…”

Section: Introduction To Dendrimers and Functional Molecular Nanopartmentioning

confidence: 99%

Self‐Assembly Behavior of Dendritic Liquid Crystals and its Implications in the Packing Structure of Functional Molecular Nanoparticles

Wang

Prakoso

2018

J Chinese Chemical Soc

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In this mini‐review, the self‐assembly characteristics of dendritic liquid crystals (LCs) are summarized. By studying and comparing the mesomorphic behavior of dendritic LCs with various core units and peripheral mesogenic units, their packing principle is established. It is found that the chirality, connecting position, and curvature of the peripheral mesogenic units play significant roles in the resulting self‐assembly structures of dendritic LCs, whereas the core symmetry and strength of intramolecular interaction affect the geometry and conformational preferences of the dendritic LCs. This fundamental knowledge gives useful guidelines to predict the self‐assembly behaviors of novel functional molecular nanoparticles, which share very similar molecular architecture with dendritic LCs.

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Conformational Preferences and the Phase Stability of Fullerene Hexa‐adducts

Cited by 6 publications

References 41 publications

Connecting Molecular and Supramolecular Shapeshifting by the Ostwald’s Nucleation Stages of a Star Giant Molecule

Connecting Molecular and Supramolecular Shapeshifting by the Ostwald’s Nucleation Stages of a Star Giant Molecule

Composition-Driven Structural Modulation and Guest-Induced Nanotemplate Effects of the Host–Guest Complexes Made by a Unimolecular Q-Clip

Self‐Assembly Behavior of Dendritic Liquid Crystals and its Implications in the Packing Structure of Functional Molecular Nanoparticles

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