High‐Fidelity Multistate Switching with Anion–Anion and Acid–Anion Dimers of Organophosphates in Cyanostar Complexes

Zhao, Wei; Qiao, Bo; Chen, Chun‐Hsing; Flood, Amar H.

doi:10.1002/ange.201707869

Cited by 9 publications

(4 citation statements)

References 57 publications

(28 reference statements)

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“…Similar distances were observed with 2:2 complexes between cyanostar and water-bridged salicylate. 102 Shorter P•••P distances, ~4 Å, 26,63 can be supported inside cyanostar assemblies 104 when stabilized by AEHBs 64 as opposed to water bridges. 102 The CH•••Odistances between cyanostar and phosphate are 4.4 Å on average consistent with weak hydrogen bonding.…”

Section: Intramolecular Rings Stabilized By Hydroxyl-to-phosphate Oh•••o -Hydrogen Bondsmentioning

confidence: 99%

“…A variation in stoichiometry with substitution was also seen in the binding to cyanostar macrocycles. 26,63 Therein, with H2PO4alone, 26 formation of divergent anti-electrostatic hydrogen bonds (AEHBs) 64 between multiple anions produced a mixture in solution composed of higher-order complexes with a range of cyanostar-anion ratios (4:3, 3:3, 3:2, 2:2, 2:1) depending on the conditions in solution. Phosphates monosubstituted with bulky naphthyl groups 63 simplified the behavior by forming only a 2:2 species with convergent AEHBs.…”

Section: Introductionmentioning

confidence: 99%

“…26,63 Therein, with H2PO4alone, 26 formation of divergent anti-electrostatic hydrogen bonds (AEHBs) 64 between multiple anions produced a mixture in solution composed of higher-order complexes with a range of cyanostar-anion ratios (4:3, 3:3, 3:2, 2:2, 2:1) depending on the conditions in solution. Phosphates monosubstituted with bulky naphthyl groups 63 simplified the behavior by forming only a 2:2 species with convergent AEHBs. Disubstituted phosphates cannot support AEHBs and thus dibutyne and dipropyne substituted phosphates formed [3]pseudorotaxanes with cyanostar macrocycles 25 in a 2:1 stoichiometry consistent with sizeselective binding of aprotic anions.…”

Section: Introductionmentioning

confidence: 99%

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Chain Entropy Beats Hydrogen Bonds to Unfold and Thread Dialcohol Phosphates inside Cyanostar Macrocycles To Form [3]Pseudorotaxanes

et al. 2021

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The recognition of substituted phosphates underpins many processes including DNA binding, enantioselective catalysis, and recently template-directed rotaxane synthesis. Beyond ATP and a few commercial substrates, however, little is known about how substituents effect organophosphate recognition. Here, we examined alcohol substituents and their impact on recognition by cyanostar macrocycles. The organophosphates were disubstituted by alcohols of various chain lengths, dipropanol, dihexanol, and didecanol phosphate, each accessed using modular solid-phases syntheses. Based on the known size-selective binding of phosphates by πstacked dimers of cyanostars, threaded [3]pseudorotaxanes were anticipated. While seen with butyl substituents, pseudorotaxane formation was disrupted by competitive OH•••Ohydrogen bonding between both terminal hydroxyls and the anionic phosphate unit. Crystallography also showed formation of a backfolded propanol conformation resulting in 8-membered ring and a perched cyanostar assembly. Motivated by established entropic penalties accompanying ring formation, we reinstated [3]pseudorotaxanes by extending the size of the substituent to hexanol and decanol. Chain entropy overcomes the enthalpically favored OH•••Ocontacts to favor random-coil conformations required for seamless, high-fidelity threading of dihexanol and didecanol phosphates inside cyanostar. These studies highlight how chain length and functional groups on phosphate's substituents can be powerful design tools to regulate binding and control assembly formation during phosphate recognition.

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Section: Intramolecular Rings Stabilized By Hydroxyl-to-phosphate Oh•••o -Hydrogen Bondsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Chain Entropy Beats Hydrogen Bonds to Unfold and Thread Dialcohol Phosphates inside Cyanostar Macrocycles To Form [3]Pseudorotaxanes

et al. 2021

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“…Flood and collaborators have reported an acid-based multistate switching of organophosphates in cyanostar complexes, which could be used in the future as potential receptors for the binding and release of organophosphates. 200 Phosphates oligomerization in cyanostar macrocycles induced formation of stackable higher order assemblies. 201 The principle concept can be expanded in the future to create molecular assemblies for phosphates recognition upon complexation.…”

Section: Acs Sustainable Chemistry and Engineeringmentioning

confidence: 99%

Nanoporous Sorbents for the Removal and Recovery of Phosphorus from Eutrophic Waters: Sustainability Challenges and Solutions

Othman

Dumitrescu

Andreescu

et al. 2018

ACS Sustainable Chem. Eng.

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Increased industrial and agricultural activity has affected the availability of phosphorus (P) in nature and has caused a significant imbalance in the P cycle with long-term consequences on ecosystem health and sustainability. While P is an essential element for food production as well as plant and animal nutrition, it is also a limited nonrenewable resource whose availability is expected to decrease in the next century. Widespread application of P-based fertilizers and their excessive accumulation in water bodies leads to eutrophication which is associated with overgrowth of harmful algal blooms and degradation of water quality. This paper provides an overview of contemporary challenges and methodologies for improving P use efficiency and sustainability in the environment. Technologies and processes for the removal of P-containing compounds from water through the use of functional nanomaterial sorbents with tailored surface properties for capture, removal, and recycling are described. Various classes of materials including carbon-based, zeolites, mesoporous silica, metal organic frameworks, metal oxides and hydroxides, biomass-derived materials, and P-binding receptors are reviewed along with their properties, binding affinity, and adsorption capacity. The potential of these materials to control the amount of P in the environment and create decision support tools for water resource management is also discussed, with examples of applications.

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Host–Host Interactions Control Self‐assembly and Switching of Triple and Double Decker Stacks of Tricarbazole Macrocycles Co‐assembled with anti‐Electrostatic Bisulfate Dimers

Dobscha

Debnath

Fadler

et al. 2018

Chemistry A European J

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Hierarchical assembly provides a route to complex architectures when using building blocks with strong and structurally well-defined recognition elements. These rules are traditionally expressed using cationic templates with reliable metal-ligand bonding but use of anions is rare on account of weak anion-host contacts. We investigate an approach that relies on host-host interactions to fortify assemblies formed between bisulfate anion dimers, [HSO4⋅⋅⋅HSO4] , and shape-persistent macrocycles called tricarbazole triazolophanes. These macrocycles have significant self-association. In chloroform, they form high fidelity, triple-decker stacks with bisulfate dimers. The strength of host-host interactions allows for preferential formation of the 3:2 tricarb:bisulfate architecture over an ion-paired architecture seen with analogous macrocycles with much weaker self-association. Solvent was expected and found to tune host-host contacts enabling formation of a 2:2 complex and solvent-driven switching between triple- and double-stacked structures. Crystallography of the 2:2:2 complex supports the idea that significant host-host interactions with tricarb arises from dipole-stabilized π-stacking. Computational studies were also conducted further highlighting the importance of host-host interactions in stacked complexes of tricarb. These findings unambiguously verify the importance of host-host interactions in the assembly and stability of discrete, responsive anion-templated architectures.

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High‐Fidelity Multistate Switching with Anion–Anion and Acid–Anion Dimers of Organophosphates in Cyanostar Complexes

Cited by 9 publications

References 57 publications

Chain Entropy Beats Hydrogen Bonds to Unfold and Thread Dialcohol Phosphates inside Cyanostar Macrocycles To Form [3]Pseudorotaxanes

Chain Entropy Beats Hydrogen Bonds to Unfold and Thread Dialcohol Phosphates inside Cyanostar Macrocycles To Form [3]Pseudorotaxanes

Nanoporous Sorbents for the Removal and Recovery of Phosphorus from Eutrophic Waters: Sustainability Challenges and Solutions

Host–Host Interactions Control Self‐assembly and Switching of Triple and Double Decker Stacks of Tricarbazole Macrocycles Co‐assembled with anti‐Electrostatic Bisulfate Dimers

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