Arene–perfluoroarene interactions confer enhanced mechanical properties to synthetic nanotubes

Roesner, Emily; Asheghali, Darya; Kirillova, Alina; Strauss, Michael J.; Evans, Austin M.; Becker, Matthew L.; Dichtel, William R.

doi:10.1039/d1sc05932g

Cited by 15 publications

(12 citation statements)

References 39 publications

(45 reference statements)

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“…Conjugated π-electron systems of nanostructured aromatic macrocycles are of peculiar interests in synthetic organic chemistry because they exceptionally show the unique cyclic π conjugation with either a parallel or radial orientation of p z orbitals. − Various topologically remarkable structures have been afforded by their contorted π-systems which, in turn, induced enduring attractions in optoelectronic materials and supramolecular assemblies. − Merging the concept of molecular chirality with π-conjugated macrocyclic chemistry has recently been revitalized for emergent applications in chiral sensing, enantioselective encapsulation, three-dimensional (3D) displays, and chiroptical materials. − Despite this much attention, access to the structurally strained and rigid chiral frameworks has long been considerably challenging. Previous studies revealed that the open-chain analogues were extensively explored as the chirality could be achieved on molecular level or in the aggregated phases of assembled superstructures .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of π-Conjugated Chiral Organoborane Macrocycles with Blue to Near-Infrared Emissions and the Diradical Character of Cations

Zhao

Liu

et al. 2023

J. Am. Chem. Soc.

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Highly emissive π-conjugated macrocycles with tunable circularly polarized luminescence (CPL) have sparked theoretical and synthetic interests in recent years. Herein, we report a synthetic approach to obtain new chiral organoborane macrocycles (CMC1, CMC2, and CMC3) that are built on the structurally chiral [5]helicenes and highly luminescent triarylborane/amine moieties embedded into the cyclic systems. These rarely accessible B/N-doped main-group chiral macrocycles show a unique topology dependence of the optoelectronic and chiroptical properties. CMC1 and CMC2 show a higher luminescence dissymmetry factor (g lum) together with an enhanced CPL brightness (B CPL) as compared with CMC3. Electronic effects were also tuned and resulted in bathochromic shifts of their emission and CPL responses from blue for CMC1 to the near-infrared (NIR) region for CMC3. Furthermore, chemical oxidations of the N donor sites in CMC1 gave rise to a highly stable radical cation (CMC1 ·+ SbF 6 –) and diradical dication species (CMC1 2·2+ 2SbF 6 –) that serve as a rare example of a positively charged open-shell chiral macrocycle.

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Section: Introductionmentioning

confidence: 99%

Synthesis of π-Conjugated Chiral Organoborane Macrocycles with Blue to Near-Infrared Emissions and the Diradical Character of Cations

Zhao

Liu

et al. 2023

J. Am. Chem. Soc.

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“…(D) Probing the impacts of arene–perfluoroarene interactions on nanotube mechanical strength. Adapted and reprinted with permission from refs , , and . Copyrights 2018 NAS, 2019 John Wiley and Sons, and 2022 Royal Society of Chemistry, respectively.…”

Section: Discussionmentioning

confidence: 99%

“…After developing a general approach to macrocyclization and 1D assembly, which enabled the high-yielding synthesis of many different macrocycles, we recognized an opportunity to further augment cohesive energies between macrocycles by installing additional noncovalent interactions. Specifically, we prepared pentagonal macrocycles from PDA and 2,3,5,6-tetrafluoroterephthalaldehyde (F 4 –PDA) and mixed them in a 1:1 ratio to invoke quadrupolar arene-perfluoroarene (AP) interactions within the macrocycle assemblies . First, we noticed that nanotubes prepared from mixed macrocycle systems were more crystalline than F 4 –PDA or PDA macrocycles alone because of the AP interactions that reinforced the structure.…”

Section: Discussionmentioning

confidence: 99%

“…Specifically, we prepared pentagonal macrocycles from PDA and 2,3,5,6-tetrafluoroterephthalaldehyde (F 4 −PDA) and mixed them in a 1:1 ratio to invoke quadrupolar arene-perfluoroarene (AP) interactions within the macrocycle assemblies. 51 First, we noticed that nanotubes prepared from mixed macrocycle systems were more crystalline than F 4 −PDA or PDA macrocycles alone because of the AP interactions that reinforced the structure. Additionally, touch- spun nanofibers of nanotubes with AP interactions exhibited a Young's modulus of 2.10 GPa, a nearly 2-fold increase relative to those of nanotube nanofibers bearing solely aromatic (1.09 GPa) or perfluoroaromatic (0.49 GPa) residues (Figure 6D).…”

Section: Mechanical Properties Of Synthetic Nanotubesmentioning

confidence: 99%

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Divergent Nanotube Synthesis through Reversible Macrocycle Assembly

et al. 2022

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Metrics & MoreArticle RecommendationsCONSPECTUS: Nanotubes offer a unique combination of structural precision, tunable interior environments, and high aspect ratios that will be useful for many applications. Despite these desirable attributes, widespread explorations into the properties and applications of chemically designed nanotubes have been limited by challenges related to their synthesis. This realization has motivated developing a unified synthetic nanotube design, which would enable wide-reaching explorations into onedimensional molecular architectures. In principle, supramolecular polymerization is a viable method to prepare such systems, but historically, this approach has yielded materials with poor mechanical properties and/or low aspect ratios whose chemical diversity is limited. This Account describes the development of an acid-mediated approach to macrocycle assembly that overcomes these limitations to yield robust, yet reversible, high-aspect-ratio nanotubes. Imine-linked macrocycles are prepared in high yield from readily accessible precursors by coupling dynamic imine exchange to an out-of-equilibrium macrocycle stacking event. Upon protonation, these macrocycles assemble into high-aspect-ratio nanotubes through electrostatic, solvophobic, and π−π interactions. The interplay between covalent and noncovalent processes are critical to guide macrocycle synthesis and assembly. Including basic pyridine groups into the macrocycle backbone leads to cooperative assembly, even in the presence of <1 equiv of acid per macrocycle. This design was elaborated to enable a general onepot nanotube synthesis from many functional aromatic dialdehydes. The development of structure−property relationships for nanotube assembly strength and ion conductivity are made possible because protonation-induced macrocycle assembly is modular and robust. For instance, supramolecular interactions endow synthetic nanotubes with robust cohesion and mechanical properties that surpass many covalent linear polymers. Tailoring the nanotube interior using site-selective chemical functionalization results in ion-conducting materials. Pyridinium-based nanotubes universally exhibit the ability to conduct protons and nanotubes functionalized with interior glycol groups promote efficient Li-ion transport. Overall, this versatile class of one-dimensional nanostructures shows substantial promise to merge the desirable properties of carbon nanotubes and biological filaments, all while being synthetically tailorable for many designed applications.

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“…Reaching inner pore diameters that are smaller and better defined, more compatible with molecular dimensions, requires other strategies that make use of more sophisticated molecules and directional noncovalent interactions. For instance, covalent macrocycles can be made to orderly stack on top of each other, often aided by peripheral H-bonding units, to form cylindrical structures with well-defined pores (Figure a, left). − Alternatively, relatively flexible linear oligomers can be made to fold intramolecularly into helical structures ( i . e ., foldamers; Figure a, right), which can also present available internal channels.…”

Section: Introductionmentioning

confidence: 99%

Stacked or Folded? Impact of Chelate Cooperativity on the Self-Assembly Pathway to Helical Nanotubes from Dinucleobase Monomers

González-Sánchez,

Mayoral,

Vázquez-González

et al. 2023

J. Am. Chem. Soc.

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Self-assembled nanotubes exhibit impressive biological functions that have always inspired supramolecular scientists in their efforts to develop strategies to build such structures from small molecules through a bottom-up approach. One of these strategies employs molecules endowed with self-recognizing motifs at the edges, which can undergo either cyclization−stacking or folding−polymerization processes that lead to tubular architectures. Which of these self-assembly pathways is ultimately selected by these molecules is, however, often difficult to predict and even to evaluate experimentally. We show here a unique example of two structurally related molecules substituted with complementary nucleobases at the edges (i.e., G:C and A:U) for which the supramolecular pathway taken is determined by chelate cooperativity, that is, by their propensity to assemble in specific cyclic structures through Watson−Crick pairing. Because of chelate cooperativities that differ in several orders of magnitude, these molecules exhibit distinct supramolecular scenarios prior to their polymerization that generate self-assembled nanotubes with different internal monomer arrangements, either stacked or coiled, which lead at the same time to opposite helicities and chiroptical properties.

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Arene–perfluoroarene interactions confer enhanced mechanical properties to synthetic nanotubes

Abstract: Supramolecular nanotubes prepared through macrocycle assembly offer unique properties that stem from their long-range order, structural predictability, and tunable microenvironments. However, assemblies that rely on weak non-covalent interactions often have...

Cited by 15 publications

References 39 publications

Synthesis of π-Conjugated Chiral Organoborane Macrocycles with Blue to Near-Infrared Emissions and the Diradical Character of Cations

Synthesis of π-Conjugated Chiral Organoborane Macrocycles with Blue to Near-Infrared Emissions and the Diradical Character of Cations

Divergent Nanotube Synthesis through Reversible Macrocycle Assembly

Stacked or Folded? Impact of Chelate Cooperativity on the Self-Assembly Pathway to Helical Nanotubes from Dinucleobase Monomers

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