Transformation networks of metal–organic cages controlled by chemical stimuli

Benchimol, Élie; Nguyen, TB; Ronson, Tanya K.; Nitschke, Jonathan R.

doi:10.1039/d0cs00801j

Cited by 86 publications

(49 citation statements)

References 174 publications

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“…Also, the Pd(II)−pyridyl ligand bond is known to be labile; as a result, the Pd(II) based assemblies could undergo cage-to-cage transformations even at ambient conditions. 41 Hence, at this point, we presume that the combination of the high binding affinity of the cage towards halides and the Pd(II)−ligand bond dynamics could be the reason for the dehalogenation ability of the cage. Subsequently, to elucidate the role of dynamic nature of the cage 1⋅4BF4 in facilitating the dehalogenation reaction, we prepared the analogues Pt(II)-based cage, 1 Pt ⋅4BF4 as the Pt(II)−Npyridyl coordination bonds are kinetically inert at ambient conditions.…”

Section: Dynamic Nature Of Pd2l4 Cagementioning

confidence: 90%

Nanoconfinement Effect: A Dynamic and Powerful Halide-Sequestrating Pd2L4 Cage

Sivalingam

Chand

2023

Preprint

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Inspired by the dehalogenase enzyme’s remarkable ability to cleave the stronger carbon-halogen bonds, we demonstrate unprecedented C−Cl bond scission using a halide-binding synthetic host. We achieved this by employing a precisely designed Pd2L4-type coordination cage equipped with Pd(II)−ligand bond dynamics and a tailor-made cage cavity with noncovalent binding forces for high-affinity anion-binding. This cage is one of the strongest chloride-binding synthetic hosts (Ka(Cl) > 1010 M−1) known in polar solvent medium. It also demonstrates at least two orders of magnitude higher chloride affinity than halophilic Ag(I) in acetonitrile. One of the fascinating features of this well-defined cage is its ability to cleave B−F/C−Cl bond in a facile manner from BF4/chlorinated solvents in nonpolar solvent media. We propose a partial cage dissociative mechanistic pathway based on experimental evidences for cage-promoted carbon−halogen bond scission.

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Section: Dynamic Nature Of Pd2l4 Cagementioning

confidence: 90%

Nanoconfinement Effect: A Dynamic and Powerful Halide-Sequestrating Pd2L4 Cage

Sivalingam

Chand

2023

Preprint

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“…[42,47] The cages can further undergo a structural transformation in response to external stimuli of the anion. [48,49] However, the choice of anions, either as a template or as a guest, in the chiral self-sorting of metal-organic cages has not been examined so far. Further, anion exchange has not been explored as a stimulus for the induced-fit structural transformation between diastereomers of different chiral self-sorting outcomes.…”

Section: (Sssr)mentioning

confidence: 99%

Anion‐Driven Programmable Chiral Self‐Sorting in Metal‐Organic Cages and Structural Transformations between Heterochiral and Homochiral Cages

Ghorai

Natarajan

2022

Chemistry A European J

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When a racemic mixture of chiral building blocks self‐assembles to form discrete molecular or supramolecular cages, the system can adopt either social or narcissistic chiral self‐sorting. However, control over such chiral self‐sorting is hard to achieve with a desired choice of outcome. Herein, we report anion templated high‐fidelity chiral self‐sorting during the coordination‐driven self‐assembly of [Pd2L4] metal‐organic cages, with a racemic mixture of an axially chiral ligand. Upon varying the counter‐anions, the outcome of the choice of chiral self‐sorting, whether social or narcissistic, leading to kinetically favored heterochiral or thermodynamically favored homochiral cages, can be controlled through specific anion encapsulation. Non‐encapsulating anion afforded a mixture of all possible diastereomers. Anion exchange enabled structural transformations between the diastereomers and the conversion of the mixture of diastereomers into homochiral diastereomers.

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“…Labile and inert metal‐organic compounds have been crucial in recent developments of supramolecular chemistry [19–21] . Phenylpyridine (phpy) derivatives are important in the synthesis of cyclometalated complexes (e.g., with Au III , Ir III , Pt II , and Pd II ) [22–25] .…”

Section: Figurementioning

confidence: 99%

Cycling a Tether into Multiple Rings: Pt‐Bridged Macrocycles for Differentiated Guest Recognition, Pseudorotaxane Transformations, and Guest Capture and Release

et al. 2022

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Macrocycle engineering is a key topic in supramolecular chemistry. When synthesizing a ring, one can obtain either complex mixtures of macrocycles of different sizes or a single ring if a template is utilized. Here, we unite these approaches along with postsynthetic modifications to transform a single tether into multiple rings-up to five per tether. The macrocycles contain two bridged phenylpyridine ligands that are connected through a Pt atom, which defines the rings' shape, size, and host activity. All rings undergo redox reactions (between Pt II and Pt IV ) that allow for large conformational changes. Their reactivity, together with their host performance, is a convenient way to control the capture and release of guests, to mediate ring transformations, and to control pseudorotaxane-to-pseudorotaxane conversions. This novel approach could serve to assemble other libraries of small ring molecules, create cyclic polymers bridged by responsive-at-metal nodes, and produce processable mechanically interlocked molecules. Since Pedersen's seminal work on crown ethers, [1,2] the synthesis of macrocycles has been central to supramolecular chemistry. [3] The library of known ring molecules is vast, encompassing diverse compositions, geometries and sizes. [4][5][6][7][8][9] Macrocycles are being investigated for applications [10] such as sensing, [11] molecular delivery, [12] molecular machinery, [13] and more. [14] Macrocycle synthesis relies on one of the approaches depicted in Figure 1. The statistical approach proceeds under kinetic control and yields mixtures of linear and cyclic oligomers; [15] template-assisted syntheses operate under thermodynamic control, favoring one particular ring; [16] and post-synthetic modifications serve to alter preassembled rings. [17,18] Although these approaches are used disjointedly, we envisioned that by applying all three in tandem, a single precursor-the tether-could be transformed into multiple rings. Forming and isolating many macrocycles from one tether is not only economical but can also lead to rings with distinct cavity sizes, and hence differentiated host activity.Labile and inert metal-organic compounds have been crucial in recent developments of supramolecular chemistry. [19][20][21] Phenylpyridine (phpy) derivatives are important in the synthesis of cyclometalated complexes (e.g., with

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Transformation networks of metal–organic cages controlled by chemical stimuli

Abstract: This review highlights transformation networks created with coordination cages. Such synthetic stimuli-controlled networks can help elucidate biological signal transduction, as well as enabling new functions and applications.

Cited by 86 publications

References 174 publications

Nanoconfinement Effect: A Dynamic and Powerful Halide-Sequestrating Pd2L4 Cage

Nanoconfinement Effect: A Dynamic and Powerful Halide-Sequestrating Pd2L4 Cage

Anion‐Driven Programmable Chiral Self‐Sorting in Metal‐Organic Cages and Structural Transformations between Heterochiral and Homochiral Cages

Cycling a Tether into Multiple Rings: Pt‐Bridged Macrocycles for Differentiated Guest Recognition, Pseudorotaxane Transformations, and Guest Capture and Release

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