Regioisomeric Tandem Triblock Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxanes

Shao, Yu; Yin, Hang; Jin, Pengfei; Jiang, Yusheng; Shen, Yang; Zhang, Wenbin

doi:10.1002/chem.201800895

Cited by 13 publications

(11 citation statements)

References 43 publications

(29 reference statements)

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“…Bulk crystallization prevents the formation of such single crystals, and thus, they are not further investigated. Our previous studies on double-chain giant surfactants (DPOSS-2PS n ) showed the opposite order of phase stability with the ortho -isomer being the most stable one in most cases ( ortho- > meta- > para- ), ,, which may seem contradictory to the current result at first glance. However, a second thought would clarify that the underlying principles are similar.…”

Section: Resultscontrasting

confidence: 99%

“…This “molecular Lego” approach is powerful in preparing monodisperse giant molecules with high molecular weight and controlled sequences and topology. − Among these molecules, POSS compounds stand out due to their high molecular symmetry and multiple vertices that can be easily functionalized. Based on the T 8 -POSS scaffold, many Janus derivatives have been prepared, such as monoadducts, regioisomeric diadducts and triadducts, , and even the tetra-adduct regioisomers. , We have previously achieved the successful separation of different regioisomers in moderate yields which facilitates the study of their structure–property relationships. , It has been shown that the regioconfiguration does exert a profound influence on the self-assembly of regioisomeric giant surfactants and shape amphiphiles, causing systematic changes in phase structure and phase stability. − It remains to be demonstrated if such effects are general to other giant molecules, such as the molecular Janus particles. ,, …”

Section: Introductionmentioning

confidence: 99%

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Symmetry-Dictated Mesophase Formation and Phase Diagram of Perfluorinated Polyhedral Oligomeric Silsesquioxanes

Shao

Yin

et al. 2019

Macromolecules

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We report the symmetry-dictated mesophase formation and phase diagram of a series of T 8 -polyhedral oligomeric silsesquioxane (POSS) derivatives bearing perfluoroalkyl chains and hydroxyl alkyl groups. The phase structures and phase behaviors of these molecular Janus particles were studied by DSC, POM, FT-IR, and WAXD experiments. It was found that introducing one hydroxyl alkyl group leads to a decreased crystal melting point, and incorporating two hydroxyl alkyl groups at different POSS positions causes the formation of lamellar liquid crystal mesophases with feature sizes and transition temperatures that depend on the symmetry of these regioisomers. Interestingly, installing only one substituent with two hydroxyl groups leads to monotropic phase transitions, where the mesophase appears only upon cooling from the isotropic melt within the narrow supercooling window. Phase diagrams were systematically constructed for these compounds and understood based on the fine influence of symmetry on their possible molecular packing scheme and their distinct hydrogen bonding patterns, as evidenced by their infrared spectra at different temperatures. These results are not only fundamental to understanding the effects of regioisomerism on giant molecule self-assembly but also important for the development of hybrid materials with tailored nanostructures.

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Section: Resultscontrasting

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Symmetry-Dictated Mesophase Formation and Phase Diagram of Perfluorinated Polyhedral Oligomeric Silsesquioxanes

Shao

Yin

et al. 2019

Macromolecules

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“…It was speculated that, unlike coil‐like PS, the rigid BPOSS could hardly deform to compensate for the unfavorable configuration for packing in the meta ‐isomer. The use of non‐crystalline tert‐butyl ‐functionalized POSS ( t BPOSS) and crystalline rod‐like fluoroalkyl‐functionalized POSS (FPOSS) gives a different set of anisotropic shape amphiphiles, FPOSS‐2 t BPOSS . In this case, only the ortho ‐isomer could form ordered lamellar structures, the other two isomers are amorphous (Figure b).…”

Section: Regio‐isomersmentioning

confidence: 99%

Macromolecular Isomerism in Giant Molecules

Shao

Shen

Zhang

2020

Chemistry A European J

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Macromolecular isomerism has been an important yet largely understudied subject. Giant molecules based on molecular nanoparticles exhibit properties highly dependent on the primary structures, providing a platform for such studies. Various isomers have been designed, synthesized and characterized, including sequence‐, regio‐, and topo‐isomers. The self‐assembly of these isomers is influenced by the distinct symmetry and collective interaction of each building block in a subtle and delicate way. The results suggest that isomerism may be exploited as a new way for fine‐tuning the structures and properties of macromolecules, which should be of great interest in both fundamental research and technical innovation.

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“…Adding a third block to the shape amphiphile would be anticipated to generate even more complexity and diversity [26]. For example, tandem triblock shape amphiphilic regio-isomers based on POSS were found to exhibit distinct self-assembling behaviors [27]. If the third block is of distinct shape, the situation would be even more interesting.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Self-Assembly and Characterization of Tandem Triblock BPOSS-PDI-X Shape Amphiphiles

et al. 2019

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In this article, we report the facile synthesis, self-assembly, and characterization of shape amphiphiles (BPOSS-PDI-X) based on isobutyl-functionalized polyhedral oligomeric silsesquioxane (BPOSS), perylene tetracarboxylic diimide (PDI), and (60)fullerene (C60) moieties. Firstly, an asymmetrically functionalized diblock shape amphiphile precursor (BPOSS-PDI-OH) was obtained through the one-pot reaction between perylene-3,4,9,10-tetracarboxylic dianhydride and two different amines, namely BPOSS-NH2 and 3-amino-1-propanol. It was further conjugated with C60-COOH to give a tri-block shape amphiphile (BPOSS-PDI-C60). Their chemical structures were thoroughly characterized by NMR, IR and MALDI-TOF MS spectrometry. In order to gain insights on the structure-property relationship, their self-assembly in gas phase, in solution, and in solid state were characterized using traveling wave ion mobility mass spectrometry (TWIM-MS), UV/Vis absorption, fluorescence emission spectrophotometer, and transmission electron microscopy, respectively. It was found that BPOSS-PDI-OH formed more complicated dimers than BPOSS-PDI-C60. Both samples showed unique aggregation behaviors in solution with increasing concentration, which could be attributed neither to H- nor to J-type and might be related to the discrete dimers. While BPOSS-PDI-C60 could hardly crystalize into ordered structures, BPOSS-PDI-OH could form nanobelt-shaped single crystals, which may hold potential applications in microelectronics.

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Regioisomeric Tandem Triblock Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxanes

Cited by 13 publications

References 43 publications

Symmetry-Dictated Mesophase Formation and Phase Diagram of Perfluorinated Polyhedral Oligomeric Silsesquioxanes

Symmetry-Dictated Mesophase Formation and Phase Diagram of Perfluorinated Polyhedral Oligomeric Silsesquioxanes

Macromolecular Isomerism in Giant Molecules

Synthesis, Self-Assembly and Characterization of Tandem Triblock BPOSS-PDI-X Shape Amphiphiles

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