Polymer networks of imine-crosslinked metal–organic cages: tuneable viscoelasticity and iodine adsorption

Schneider, Matthew L.; Campbell, Jonathan A.; Slattery, Ashley; Bloch, Witold M.

doi:10.1039/d2cc04969d

Cited by 12 publications

(15 citation statements)

References 48 publications

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“…The reaction was adapted from a previously reported procedure . To a 20 mL scintillation vial was added Mg-NH 2 (100 mg, 0.02 mmol) and solvated in DMF (10 mL).…”

Section: Methodsmentioning

confidence: 99%

Postsynthetic Modification of Calixarene-Based Porous Coordination Cages

Dworzak,

Sampson,

Montone

et al. 2024

Chem. Mater.

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Porous coordination cages have garnered considerable interest as a distinct class of permanently porous materials due to their unique molecular nature, setting them apart from more traditional metal−organic materials, including metal−organic frameworks. Postsynthetic modification (PSM) of cages offers a promising avenue for tailoring their properties, but challenges remain, including maintaining solubility, functional group compatibility and stability, and potential changes in porosity. Here, we explore novel approaches to address these challenges and enhance the versatility of coordination cages. We initially targeted alkylation and acylation reactions, where anhydrides were ultimately employed as relatively mild reagents. To expand the toolkit of PSM reactions, we explored Pd-catalyzed cross-coupling reactions, where high-throughput methodologies were used to optimize reaction conditions. In this regard, we identify Pd(OAc) 2 with a 1,1′-bis(di-tert-butylphosphino)ferrocene ligand as an efficient reagent for the PSM of aryl-bromide functionalized cages with arylboronic acids. Overall, this work broadens the scope of the PSM of cages and highlights its potential as an avenue to tailor cages for specific applications in gas adsorption, separation, and catalysis.

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“…The reaction was adapted from a previously reported procedure . To a 20 mL scintillation vial was added Mg-NH 2 (100 mg, 0.02 mmol) and solvated in DMF (10 mL).…”

Section: Methodsmentioning

confidence: 99%

Postsynthetic Modification of Calixarene-Based Porous Coordination Cages

Dworzak,

Sampson,

Montone

et al. 2024

Chem. Mater.

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“…Bloch demonstrated the synthesis of amine-functionalized Cu 24 L 24 cages that turn into gels upon dialdehyde addition. [16] The connection of organic cages via organic linkers can lead to the formation of cage based covalent organic frameworks. Examples of such frameworks have been reported by Wang or Chen, Little and Cooper.…”

Section: Introductionmentioning

confidence: 99%

“…The connection of cages via exohedral functionalization may also result in the formation of polymeric structures. Bloch demonstrated the synthesis of amine‐functionalized Cu 24 L 24 cages that turn into gels upon dialdehyde addition [16] . The connection of organic cages via organic linkers can lead to the formation of cage based covalent organic frameworks.…”

Section: Introductionmentioning

confidence: 99%

Reactions in Endohedral Functionalized Cages

Otte

2023

Eur J Org Chem

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The introduction of enhanced functionalization is a key aspect in the current design of cage chemistry. At the moment, several approaches are intensively investigated. The synthesis of cage compounds that display endohedral functionalization plays a key role among them. Here, the studies of reactions that occur in endohedral‐functionalized cage compounds is reviewed. After an introduction in current trends in cage‐chemistry the discussion of reactions in endohedral‐cage compounds is divided into three sections. These are: 1) Endohedral groups that are by themselves functional, 2) endohedral groups that can bind to a transition‐metal complex and 3) endohedral groups that can bind by themselves to a metal. The article closes with an outlook on additional current developments in the field of endohedral‐functionalized cage‐compounds, which may contribute in the future towards reactivity in cage compounds.

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“…The presence of Lewis acids or bases would interact with the amine or Cu sites, whereby the CuMOPs showed considerable stability. 44 It is rather difficult to dissociate the as-formed coordinates under mild conditions. Some strong bases such as bipyridine 45 or imidazole, 46 after coassembly with Cu-MOPs, would well maintain the basic structures.…”

mentioning

confidence: 99%

“…Cu-MOPs have been widely used to construct both soft and rigid materials without a reported disassociation. The presence of Lewis acids or bases would interact with the amine or Cu sites, whereby the CuMOPs showed considerable stability . It is rather difficult to dissociate the as-formed coordinates under mild conditions.…”

mentioning

confidence: 99%

Chiral Superlattices Self-Assembled from Post-Modified Metal–Organic Polyhedra

et al. 2023

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Metal–organic polyhedra (MOPs) are inherently porous, discrete, and solvent-dispersive, and directing them into chiral superlattices through direct self-assembly remains a considerable challenge due to their nanoscale size and structural complexity. In this work, we illustrate a postmodification protocol to covalently conjugate a chiral cholesteryl pendant to MOPs. Postmodification retained the coordination cores and allowed for reaction-induced self-assembly in loosely packed nanosized columns without supramolecular chirality. Solvent-processed bottom-up self-assembly in aqueous media facilitated the well-defined packing into twisted superlattices with a 5 nm lattice parameter. Experimental and computational results validated the role of intercholesteryl forces in spinning the nanosized MOPs, which achieved the chirality transfer to supramolecular scale with chiral optics. This work establishes a novel protocol in rational design of MOP-based chiroptical materials for potential applications of enantioselective adsorption, catalysis, and separation.

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Polymer networks of imine-crosslinked metal–organic cages: tuneable viscoelasticity and iodine adsorption

Abstract: The solution structure of an amine-functionalised Cu24L24 cage (MOP-15) is elucidated which enables its direct covalent crosslinking into a series of highly tuneable organogels. These soft porous networks exhibit up...

Cited by 12 publications

References 48 publications

Postsynthetic Modification of Calixarene-Based Porous Coordination Cages

Postsynthetic Modification of Calixarene-Based Porous Coordination Cages

Reactions in Endohedral Functionalized Cages

Chiral Superlattices Self-Assembled from Post-Modified Metal–Organic Polyhedra

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