Organic Cages through Dynamic Covalent Reactions

Ding, Huimin; Chen, Rufan; Wang, Cheng

doi:10.1002/9781119075738.ch4

Cited by 4 publications

(5 citation statements)

References 99 publications

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“…(Figure 3b). All the other reaction networks for ladders with [2]-to [10]-rungs were similarly generated, as the assumptions are general for any length ladder. Each rung is assumed to independently undergo reversible opening (rung dissociation) and closing (rung association).…”

Section: ■ Model Constructionmentioning

confidence: 99%

“…8,9 Kinetic trapping occurs when the rate of constituent exchange is slower than the time scale to perform the overall reaction in the laboratory. 10 Since dynamic chemistries cover a wide kinetic range (Figure 1), the inability to converge to a thermodynamic minimum is more frequently encountered in systems with low dissociation rates. 11 Additionally, kinetic traps are also common with high-valency constituents, 12−15 owing to the low probability of simultaneously dissociating all of the bonding interactions (i.e., high avidity).…”

Section: ■ Introductionmentioning

confidence: 99%

“…Dynamic synthesis targets ordered structures made from constituents that are joined through multiple, reversible bonding sites (i.e., the constituents are multivalent with dynamic bonds). In many cases, thermodynamic modeling accurately predicts the major products since equilibrium is readily achieved. − As increasingly complex structures are targeted, persistent intermediates arise as kinetic traps, − stymieing the synthesis. , Kinetic trapping occurs when the rate of constituent exchange is slower than the time scale to perform the overall reaction in the laboratory . Since dynamic chemistries cover a wide kinetic range (Figure ), the inability to converge to a thermodynamic minimum is more frequently encountered in systems with low dissociation rates .…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Quantifying Error Correction through a Rule-Based Model of Strand Escape from an [n]-Rung Ladder

2019

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The rational design of 3D structures (MOFs, COFs, etc.) is presently limited by our understanding of how the molecular constituents assemble. The common approach of using reversible interactions (covalent or noncovalent) becomes challenging, especially when the target is made from multivalent building blocks and/or under conditions of slow exchange, as kinetic traps and nonequilibrium product distributions are possible. Modeling the time course of the assembly process is difficult because the reaction networks include many possible pathways and intermediates. Here we show that rule-based kinetic simulations efficiently model dynamic reactions involving multivalent building blocks. We studied "strand escape from an [n]-rung ladder" as an example of a dynamic process characterized by a complex reaction network. The strand escape problem is important in that it predicts the time a dynamic system needs to backtrack from errors involving [n]-misconnections. We quantify the time needed for error correction as a function of the dissociation rate coefficient, strand valency, and seed species. We discuss the simulation results in relation to a simple probabilistic framework that captures the power law dependence on the strand's valency, and the inverse relationship to the rung-opening rate coefficient. The model also tests the synthetic utility of a one-rung (i.e., hairpin) seed species, which, at intermediate times, bifurcates to a long-lived, fully formed [n]-rung ladder and a pair of separated strands. Rule-based models thus give guidance to the planning of a dynamic covalent synthesis by predicting time to maximum yield of persistent intermediates for a particular set of rate coefficients and valency.

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Section: ■ Model Constructionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Quantifying Error Correction through a Rule-Based Model of Strand Escape from an [n]-Rung Ladder

2019

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“…In particular, the reversible formation of imine bonds is affected by external factors such as temperature, pH, and concentration but also by internal factors such as steric and electronic features of the substrates. Dynamic imines have been used in different applications, including the synthesis of complex molecular architectures, such as cages, and in self-sorting systems …”

Section: Introductionmentioning

confidence: 99%

Kinetic and Thermodynamic Modulation of Dynamic Imine Libraries Driven by the Hexameric Resorcinarene Capsule

et al. 2020

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The composition of dynamic covalent imine libraries (DCL) adapts to the presence of the hexameric resorcinarene capsule. In the presence of the self-assembled capsule, a kinetic and thermodynamic modulation of the imine constituents of the DCLs was observed, which was induced by an unusual predatory action of the capsule on specific imine constituents. More complex 2 × 2 DCLs also adapt to the presence of the hexameric capsule, showing a thermodynamic and kinetic modulation of the constituents induced by the predatory action of the capsule. By cross-referencing experimental data, a good selectivity (up to 66%) for one constituent can be induced in a 2 × 2 DCL.

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“…[1] By utilizing these characteristics, it is possible to synthesize large covalent organic cages in high yield by simply mixinga ppropriate component molecules under thermodynamic conditions through self-assembly processes. [2] Since landmark reports from the groups of Atwood [3a] and Cooper [4] in 2009, organic cages have attracted much attention as novel porous materials, and variouscovalento rganic cages have been synthesized and investigated. [5] Considering practical application as porousm aterials, the reversibility of the cage framework, which would lead to its chemical instability,i sr egarded as ap roblem.…”

Section: Introductionmentioning

confidence: 99%

Dynamic Behavior of Covalent Organic Cages

Ono

Iwasawa

2018

Chemistry A European J

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Discrete, large, covalent organic cages have recently been constructed by utilizing various types of dynamic covalent bond formation. The reversibility of bond formation can provide an opportunity to exhibit unique dynamic behavior; however, the transformation of such rigid cages to other structures remains challenging. To clarify the current status of this emerging research field, this Concept article gives an overview of recent progress of the dynamic behavior of covalent organic cages by classifying them into four types of transformation, namely, dimerization into the interlocked cages, transformation into different cage structures, exchange of components, and disassembly. The driving forces of such dynamic behavior and problems to be solved are also highlighted.

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Organic Cages through Dynamic Covalent Reactions

Cited by 4 publications

References 99 publications

Quantifying Error Correction through a Rule-Based Model of Strand Escape from an [n]-Rung Ladder

Quantifying Error Correction through a Rule-Based Model of Strand Escape from an [n]-Rung Ladder

Kinetic and Thermodynamic Modulation of Dynamic Imine Libraries Driven by the Hexameric Resorcinarene Capsule

Dynamic Behavior of Covalent Organic Cages

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