Direct Visualization of Pyrrole Reactivity upon Confinement within a Cyclodextrin Metal–Organic Framework

Núñez-López, Alejandro; Galbiati, Marta; Padial, Natalia M.; Ganivet, Carolina R.; Tatay, Sergio; Pardo, Emilio; Armentano, Donatella; Martí‐Gastaldo, Carlos

doi:10.1002/anie.201904890

Cited by 16 publications

(9 citation statements)

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“…64 Martí-Gastaldo and co-workers also demonstrated the possibility of restricting the growth of polypyrrole by confined oxidation of pyrrole (Py) monomers after encapsulation in Rb-CD-MOF to generate terpyrrole (TPy) charge transfer salts (Figure 2d). 65 Whereas Rb-CD-MOF and Rb-CD-MOFPy behave as insulators (  = 10 -11 -10 -12 S•cm -1 ), Rb-CD-MOFTPy displays a million-fold enhancement of the electrical conductivity up to 5•10 -6 S•cm -1 . More recently, Ballav and co-workers polymerized PEDOT and PPy inside the pores of UiO-66.…”

Section: Infiltration Of Conductive Guestsmentioning

confidence: 99%

Electrical conductivity and magnetic bistability in metal–organic frameworks and coordination polymers: charge transport and spin crossover at the nanoscale

2020

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Section: Infiltration Of Conductive Guestsmentioning

confidence: 99%

Electrical conductivity and magnetic bistability in metal–organic frameworks and coordination polymers: charge transport and spin crossover at the nanoscale

2020

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“…During the past decade, CD-MOFs have emerged as a novel class of porous, extended frameworks owing to their robust crystallinity, permanent porosity, and excellent biocompatibility. On account of their ability to absorb guest molecules, including gases, drugs, metal-based nanoclusters, and nanoparticles, CD-MOFs have found applications in templated syntheses of metal-based nanoparticles, adsorption, , sensing, , separations, purifications, gels, electrical memories, drug delivery systems, − trapping of highly reactive intermediates, catalyst stabilization, and catalyst supports . The initial discovery of CD-MOFs and the development of the field by us in the beginning, with subsequent contributions from a growing CD-MOF community, show that these inexpensive and biocompatible materials stand a good chance of finding applications in personal and home care, as well as in the food and pharmaceutical industries.…”

Section: Introductionmentioning

confidence: 99%

Cyclodextrin Metal–Organic Frameworks and Their Applications

2021

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Metrics & MoreArticle Recommendations CONSPECTUS: Cyclodextrin-based metal−organic frameworks (CD-MOFs), derived from γ-cyclodextrin (γ-CD) and alkali metal cations, constitute a class of porous, renewable, and edible MOFs that can be synthesized from a naturally occurring carbohydrate on a large scale. γ-CD is a C 8 -symmetrical cyclic oligosaccharide composed of eight asymmetric α-1,4-linked D-glucopyranosyl residues that possesses a bucket-shaped cavity with an inner diameter of ∼1 nm and a depth of ∼0.8 nm. Upon combination of 1 equiv of γ-CD with 8 equiv of potassium hydroxide in an aqueous solution, followed by vapor diffusion of MeOH (or EtOH) into this solution during several days, CD-MOF-1 is obtained as cubic crystals. This carbohydrate-based MOF, which was discovered serendipitously in 2010, was the first highly crystalline CD-MOF to be obtained. X-ray crystallography of a single crystal reveals that it adopts the space group I432 with unit cell dimensions of approximately 31 × 31 × 31 Å 3 . Other CD-MOFs, namely, CD-MOF-2 and CD-MOF-3, can be obtained when potassium ions are replaced by rubidium and cesium ions, respectively. CD-MOFs comprise extended body-centered frameworks of (γ-CD) 6 cubic units, which contain spherical pores that reside at the center of the cubes, interconnected by alkali metal cations, forming both cylindrical and triangular channels.During the past decade, CD-MOFs have emerged as a useful class of multifunctional materials based on porous frameworks with extended structures displaying robust crystallinity, permanent porosity, and excellent biocompatibility. The family of CD-MOFs has been joined by a growing collection of metal nodes involving alkali metal cations (Li + , Na + , K + , Rb + , Cs + ) and γ-CD as well as its derivatives. As a result of the ability of their extended porous frameworks to absorb guest molecules, including gases, drugs, metalbased nanoclusters, and nanoparticles, CD-MOFs have potential applications in areas as disparate as templating syntheses of metalbased nanoparticles and gels, adsorption and separation, trapping highly reactive intermediates, catalyst supports, sensing, electrical memory, and drug delivery.In this Account, we tell the story of CD-MOFs, a scientific discovery made in our research laboratory at Northwestern University, and the opportunities to use these environmentally friendly porous materials across different fields of science and technology. The story includes representative synthetic protocols for the preparation of CD-MOFs, along with an overview of their structural features, functionalization, and chemical modification aimed at increasing their stabilities in aqueous environments, and finally, a summary of their applications. The examples we will discuss, however, are only illustrative, and there is a significant body of additional findings emanating from our laboratory and others, especially in the realm of developing new synthetic strategies, tuning the framework stabilities, and exploring the guest inclusion and emergent pro...

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“…[21,[34][35][36][37][38] Them echanism of an anoconfined polymerization occurring inside aM OF has been very recently interpreted through modeling the electron density obtained in the pores by SCXRD after performing the reaction, allowing the detection of the ionic products formed. [39] It is suggested that the MOF affects the mobility of the substrates and controls the overall reactivity of confined molecules.Inthis work, we aim to push the scope of SCXRD/CSM methods further and directly follow the evolution of asupramolecular aggregate of neutral guest molecules in the pores of aMOF,bythe interpretation of the electron density over as eries of time steps depicting as low dynamic process.Acomplete modeling of all the electron density contained in the pores of MOFs is very rarely done given the problems associated with disorder and thermal motions.H owever,w eh ere demonstrate that it is affordable and highly informative.…”

Section: Introductionmentioning

confidence: 99%

Stepwise Evolution of Molecular Nanoaggregates Inside the Pores of a Highly Flexible Metal–Organic Framework

et al. 2019

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The crystalline sponge method (CSM) is primarily used for structural determination by single‐crystal X‐ray diffraction of a single analyte encapsulated inside a porous MOF. As the host–guest systems often show severe disorder, reliable crystallographic determination is demanding; thus the dynamics of the guest entering and the formation of nanoconfined molecular aggregates has not been in the spotlight. Now, the concept is investigated of the CSM for monitoring the structural evolution of nanoconfined supramolecular aggregates of eugenol guests with displacement of DMF inside the cavities of the flexible MOF, PUM168. The interpretation of the electron density provides a series of unique detailed snapshots depicting the supramolecular guest aggregation, thus showing the tight interplay between the host flexible skeleton and the molecular guests through the DMF‐to‐eugenol exchange process.

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Direct Visualization of Pyrrole Reactivity upon Confinement within a Cyclodextrin Metal–Organic Framework

Abstract: Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Cited by 16 publications

References 30 publications

Electrical conductivity and magnetic bistability in metal–organic frameworks and coordination polymers: charge transport and spin crossover at the nanoscale

Electrical conductivity and magnetic bistability in metal–organic frameworks and coordination polymers: charge transport and spin crossover at the nanoscale

Cyclodextrin Metal–Organic Frameworks and Their Applications

Stepwise Evolution of Molecular Nanoaggregates Inside the Pores of a Highly Flexible Metal–Organic Framework

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