Self-Assembled Helical and Twisted Nanostructures of a Preferred Handedness from Achiral π-Conjugated Oligo(<i>p</i>-phenylenevinylene) Derivatives

Cui, Yinan; Tao, Dandan; Huang, Xiaoyu; Lu, Guolin; Feng, Chuanqi

doi:10.1021/acs.langmuir.8b04127

Cited by 12 publications

(12 citation statements)

References 54 publications

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“…The helical structure is a sophisticated, ubiquitous motif that is found in biological systems, the conformation of which is related to the chirality that is caused by supramolecular assembling. In some synthetic systems, helical supramolecular assemblies can be formed from highly anisotropic achiral amphiphiles, which contain rigid aromatic moieties [ 71 , 103 , 104 , 105 , 106 ], without external symmetry-breaking inducing factors. In all these cases, but especially for block copolymers [ 71 , 105 , 107 ], the occurrence of symmetry breaking is subtle and depends on both the molecular structure and external environmental factors.…”

Section: Resultsmentioning

confidence: 99%

3,4-Ethylenedioxythiophene (EDOT) End-Group Functionalized Poly-ε-caprolactone (PCL): Self-Assembly in Organic Solvents and Its Coincidentally Observed Peculiar Behavior in Thin Film and Protonated Media

Bendrea¹,

Cianga²,

Ailiesei³

et al. 2021

Polymers

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End-group functionalization of homopolymers is a valuable way to produce high-fidelity nanostructured and functional soft materials when the structures obtained have the capacity for self-assembly (SA) encoded in their structural details. Herein, an end-functionalized PCL with a π-conjugated EDOT moiety, (EDOT-PCL), designed exclusively from hydrophobic domains, as a functional “hydrophobic amphiphile”, was synthesized in the bulk ROP of ε-caprolactone. The experimental results obtained by spectroscopic methods, including NMR, UV-vis, and fluorescence, using DLS and by AFM, confirm that in solvents with extremely different polarities (chloroform and acetonitrile), EDOT-PCL presents an interaction- and structure-based bias, which is strong and selective enough to exert control over supramolecular packing, both in dispersions and in the film state. This leads to the diversity of SA structures, including spheroidal, straight, and helical rods, as well as orthorhombic single crystals, with solvent-dependent shapes and sizes, confirming that EDOT-PCL behaves as a “block-molecule”. According to the results from AFM imaging, an unexpected transformation of micelle-type nanostructures into single 2D lamellar crystals, through breakout crystallization, took place by simple acetonitrile evaporation during the formation of the film on the mica support at room temperature. Moreover, EDOT-PCL’s propensity for spontaneous oxidant-free oligomerization in acidic media was proposed as a presumptive answer for the unexpected appearance of blue color during its dissolution in CDCl3 at a high concentration. FT-IR, UV-vis, and fluorescence techniques were used to support this claim. Besides being intriguing and unforeseen, the experimental findings concerning EDOT-PCL have raised new and interesting questions that deserve to be addressed in future research.

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Section: Resultsmentioning

confidence: 99%

3,4-Ethylenedioxythiophene (EDOT) End-Group Functionalized Poly-ε-caprolactone (PCL): Self-Assembly in Organic Solvents and Its Coincidentally Observed Peculiar Behavior in Thin Film and Protonated Media

Bendrea¹,

Cianga²,

Ailiesei³

et al. 2021

Polymers

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“…Twisted chiral nanotubes and nanoribbons with biased chirality were formed with these achiral components in well‐tuned solvent systems. [ 58 ] Formation of chiral structures would be driven by directional π–π stacking accompanied by the steric repulsion of poly(ethylene glycol) chains. At the initial stage, the chiral structures are originated under statistical fluctuations, which can be extended to an accidental excess of handedness in higher‐level of structures such as the ribbons and the fibers.…”

Section: Chiral Nanoarchitectonics Of Molecular Assembliesmentioning

confidence: 99%

Supramolecular Chiral Nanoarchitectonics

et al. 2020

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of well-considered materials designs. [5] Small structural differences in component molecules are often capable of producing materials with totally different properties through organic syntheses, [6] supramolecular chemistry, [7] and materials processing. [8] Therefore, molecular designs for materials production can be regarded as the most important issue in science and technology in current society. Amongst the many possibilities in molecular design for materials production, exploration of molecular functions and material properties on the basis of chirality controls would be a scientifically elegant approach. With identical elemental compositions and functional groups, but different configurations of these identical groups, functions such as chiroptical properties and chiral separations can be created. [9] Another important fact for chiral controls in molecular and materials science is the unavoidable deep relationship of chiral substances with biological activities. [10] Biomolecules are basically made of chiral components such as amino acids and saccharides. Therefore, molecular designs for biomedical drugs and bioactive materials must be produced upon critical control of their chirality. Due to the scientifically elegant approaches and biological importance, molecular sciences and materials technologies incorporating chirality continuously attract attention of scientists ranging from the fundamentals of the chirality of molecules and materials to bio-related applications. These research efforts spread into a wide range of scientific fields including basic physical chemistry, [11] chirality-controlled catalysis and synthesis, [12] chiral materials, [13] analyses of chiral structures, [14] chiral recognition, [15] chiral separation, [16] chiral plasmons and optics, [17] chiral drugs, [18] and biomedical related chiral sciences. [19] Among the broad interests of chirality research, the recent hot trends of chirality related sciences are probably studies on chirality-based supramolecular chemistry and materials science upon the self-assembly of chiral molecular components [20] and achiral building blocks. [21] Enhancement of chiral effects and the creation of chirality are sometimes results of supramolecular organizations with chiral molecular units and even with achiral components. These systems are regarded as elegant examples of the emerging concept of nanoarchitectonics (Figure 1), [22] because control of simple molecular configurations can lead to the creation of such a wide variety of functional materials. The nanoarchitectonics concept was originally proposed by Aono and co-workers [23] as methodology to create functional materials from nanosized components through the combined Exploration of molecular functions and material properties based on the control of chirality would be a scientifically elegant approach. Here, the fabrication and function of chiral-featured materials from both chiral and achiral components using a supramolecular nanoarchitectonics concept are discussed. The contents are classified...

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“…Following similar self-assembly principles, a number of rod-coil BCP systems containing other types of conjugated polymers, such as polyfluorene, [48][49][50][51] polyphenylene, 52,53 polyacetylene, 54 poly( p-phenylenevinylene) (PPV), 43,[55][56][57][58][59][60][61] and polyaniline, 62 also exhibit controllable multi-dimensional selfassembly behavior in solution. Polyfluorene-based rod-coil BCPs possess high thermal/chemical stability and good fluorescence quantum yields, and thus their self-assembly in solution is of increasing interest.…”

Section: Self-assembly Of Rod-coil Block Copolymersmentioning

confidence: 99%

“…Poly( p-phenylenevinylene) (PPV) or oligo( p-phenylenevinylene) (OPV) is also one of the well-known p-conjugated materials with intriguing optical and electronic properties. 43,[55][56][57][58][59][60][61] Based on the seeded growth strategy of living crystallization-driven selfassembly, Huang and coworkers prepared, in ethanol, 1D nanofibers of controlled lengths ranging from 50 to 870 nm with a uniform OPV core and a poly(N-isopropylacrylamide) (PNIPAM) corona (Fig. 7).…”

Section: Self-assembly Of Rod-coil Block Copolymersmentioning

confidence: 99%