Active mechanisorption driven by pumping cassettes

Feng, Liang; Qiu, Yan; Guo, Qing‐Hui; Chen, Zhijie; Seale, James S W; He, Kun; Wu, Huang; Feng, Yuanning; Farha, Omar K.; Astumian, R. Dean; Stoddart, J. Fraser

doi:10.1126/science.abk1391

Cited by 117 publications

(129 citation statements)

References 64 publications

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“…Connecting two viologen units by rigid spacers, the “Blue Box” is an archetypal aromatic-based macrocycle 12 that has found numerous applications in functional organic materials 13 and machines. 14 Other common π-conjugated components for macrocycles include porphyrins, 15 , 16 tetrathiafulvalenes, 17 , 18 and rylene diimides. 19 In the latter class, perylene diimides (PDIs) are important targets because they are robust, 20 economic organic dyes 21 with a readily functionalizable scaffold.…”

Section: Introductionmentioning

confidence: 99%

The Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle

et al. 2022

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This work showcases chiral complementarity in aromatic stacking interactions as an effective tool to optimize the chiroptical and electrochemical properties of perylene diimides (PDIs). PDIs are a notable class of robust dye molecules and their rich photo- and electrochemistry and potential chirality make them ideal organic building blocks for chiral optoelectronic materials. By exploiting the new bay connectivity of twisted PDIs, a dynamic bis-PDI macrocycle (the “Pink Box”) is realized in which homochiral PDI–PDI π–π stacking interactions are switched on exclusively. Using a range of experimental and computational techniques, we uncover three important implications of the macrocycle’s chiral complementarity for PDI optoelectronics. First, the homochiral intramolecular π–π interactions anchor the twisted PDI units, yielding enantiomers with half-lives extended over 400-fold, from minutes to days (in solution) or years (in the solid state). Second, homochiral H-type aggregation affords the macrocycle red-shifted circularly polarized luminescence and one of the highest dissymmetry factors of any small organic molecule in solution ( g lum = 10 –2 at 675 nm). Finally, excellent through-space PDI–PDI π-orbital overlap stabilizes PDI reduced states, akin to covalent functionalization with electron-withdrawing groups.

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Section: Introductionmentioning

confidence: 99%

The Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle

et al. 2022

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“…High packing densities of bistable rotaxanes 17 and catenanes embedded in self-assembled monolayers [18][19][20] and polymers 21 result in a signicant decrease in the rate of rotational and translational motion. Similar effects were observed for the intramolecular rotational motion of molecular motors embedded in polymers 7,22 or graed onto surfaces.…”

Section: Introductionmentioning

confidence: 99%

Light-driven molecular motors embedded in covalent organic frameworks

et al. 2022

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“… 33 , 34 Very recent examples include the mechanisorption driven accumulation of ring-like molecules on a MOF surface and the active transport of substrates from solution to polymer beads. 35 , 36 A key step in the development of macroscopically activated systems is the availability of methodology that provides spatial control over structure formation. 13 , 37 A promising direction is provided by reaction-diffusion systems in which diffusion of a locally applied trigger (e.g., molecules, 33 , 38 acid, 39 , 40 redox 41 , 42 ) through a hydrogel matrix activates structure formation in the matrix ( Figure 1 , top).…”

Section: Introductionmentioning

confidence: 99%

Progressive Local Accumulation of Self-Assembled Nanoreactors in a Hydrogel Matrix through Repetitive Injections of ATP

et al. 2022

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Cellular functions are regulated with high spatial control through the local activation of chemical processes in a complex inhomogeneous matrix. The development of synthetic macroscopic systems with a similar capacity allows fundamental studies aimed at understanding the relationship between local molecular events and the emergence of functional properties at the macroscopic level. Here, we show that a kinetically stable inhomogeneous hydrogel matrix is spontaneously formed upon the local injection of ATP. Locally, ATP templates the self-assembly of amphiphiles into large nanoreactors with a much lower diffusion rate compared to unassembled amphiphiles. The local depletion of unassembled amphiphiles near the injection point installs a concentration gradient along which unassembled amphiphiles diffuse from the surroundings to the center. This allows for a progressive local accumulation of self-assembled nanoreactors in the matrix upon repetitive cycles of ATP injection separated by time intervals during which diffusion of unassembled amphiphiles takes place. Contrary to the homogeneous matrix containing the same components, in the inhomogeneous matrix the local upregulation of a chemical reaction occurs. Depending on the way the same amount of injected ATP is administered to the hydrogel matrix different macroscopic distributions of nanoreactors are obtained, which affect the location in the matrix where the chemical reaction is upregulated.

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Active mechanisorption driven by pumping cassettes

Cited by 117 publications

References 64 publications

The Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle

The Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle

Light-driven molecular motors embedded in covalent organic frameworks

Progressive Local Accumulation of Self-Assembled Nanoreactors in a Hydrogel Matrix through Repetitive Injections of ATP

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