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/ange.201904890

Cited by 6 publications

(6 citation statements)

References 29 publications

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“…Previous works on the oxidative polymerization of pyrrole and EDOT reported that the conductivity of the host–polymer complexes ranges from 10 –1 to 10 –7 S cm –1 depending on the morphology and properties of the host (MOFs, PCPs, etc.). The conductivity of the 1· PPy and 1· PEDOT complexes lies closer to the single crystals of the terpyrrole cationic polymers confined in the cyclodextrin MOFs . Considering that morphological defects (crack or bend) of the single crystals of 1· PPy and 1· PEDOT will tend to lower their conductance, the conductivity values observed here may represent a lower bound on what is achievable.…”

Section: Resultsmentioning

confidence: 58%

“…PPy is a simple and well-studied example, which undergoes polymerization through radical cationic intermediates . The rapid rate of the reaction affords primarily α-α′ connections as well as other C–C couplings, which lead to crosslinking that can modulate the conductivity of the resulting polymer. , The polymerization of pyrrole has been studied in numerous confined spaces including in zeolites, AAOs, MOFs, , and in coordination nanochannels . Similarly, PEDOT has been synthesized in the pores of porous coordination polymers, , nanochannels, , SURMOFs, and on nanoporous layer glass to increase the conductivity of these materials.…”

Section: Introductionmentioning

confidence: 99%

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Inclusion Polymerization of Pyrrole and Ethylenedioxythiophene in Assembled Triphenylamine Bis-Urea Macrocycles

et al. 2022

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Herein, two different monomers, pyrrole (Py) and ethylenedioxythiophene (EDOT), are loaded into a self-assembled bis-urea host 1 and oxidatively polymerized within its nanochannels, dramatically changing the properties of the crystalline complexes. Molecular dynamics (MD) simulation of both monomers within the channel demonstrates that they diffuse through the confinement upon applying thermal energy, which may facilitate the polymerization reaction. The structures of these host–guest complexes are characterized before and after polymerization using solid-state and photophysical measurements. The host maintains its columnar morphology during polymerization at 90 °C using iodine as an oxidizing agent. Intriguingly, upon dissolution of the host and recovery by filtration, the polymers exhibit memory of their nanoreactor environment, displaying unusual order by scanning electron microscopy, powder X-ray diffraction, and small- and wide-angle X-ray analysis. Solid-state 13C cross-polarized magic angle spinning NMR suggests that polypyrrole (PPy) exhibits primarily α,α′ linkages with some contributions from the quinoid form. Similarly, poly(ethylenedioxythiophene) (PEDOT) also exhibits formation of primarily α,α′ linkages with minor quinoid contributions. Both the 1·PPy and 1·PEDOT crystals show a 103-fold increase in conductivity to ∼10–6 S/cm versus host 1 crystals, which are nonconductive ∼10–9 S/cm. Overall, supramolecular polymerization strategies have the potential to readily modulate the properties of nanostructured materials.

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Section: Resultsmentioning

confidence: 58%

Section: Introductionmentioning

confidence: 99%

Inclusion Polymerization of Pyrrole and Ethylenedioxythiophene in Assembled Triphenylamine Bis-Urea Macrocycles

et al. 2022

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“…This cavity is crucial for the various encapsulation purposes of CD-MOFs. 99 Additionally, CD-MOF-1 has triangular channels of 0.4 nm size that can be observed upon orientation of the crystal structure at 45° with respect to the crystallographic axes (Fig. 4b).…”

Section: Synthesis Structure and Properties Of Cd-mof Materialsmentioning

confidence: 97%

“…This cavity is crucial for the various encapsulation purposes of CD-MOFs. 99 Additionally, CD-MOF-1 has triangular channels of Reproduced with permission. 102 Copyright 2017, American Chemical Society.…”

Section: Cd-mofsmentioning

confidence: 99%

Cyclodextrin metal–organic frameworks and derivatives: recent developments and applications

et al. 2022

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“…Metal–organic frameworks (MOFs) 1 − 3 have become a hot topic of research during the past decades due to the concomitant presence of atheistically pleasant porous high-dimensional structures with intriguing net topologies and thrilling chemical and physical properties. Indeed, these hybrid materials—consisting of metal ions (or small metal clusters) linked by a wide diversity of organic spacers—have been able to make themselves a functional entity by controlling the assembling of their subunits, which have enabled them to find applications in gas storage and separation, 4 − 6 drug delivery, 7 − 9 molecular recognition, 10 − , 14 and catalysis 15 − 18 as well as in templating the in situ growth/encapsulation of a wide variety of functional moieties 19 , 20 …”

Section: Introductionmentioning

confidence: 99%

A Biocompatible Aspartic-Decorated Metal–Organic Framework with Tubular Motif Degradable under Physiological Conditions

et al. 2021

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Achieving a precise control of the final structure of metal–organic frameworks (MOFs) is necessary to obtain desired physical properties. Here, we describe how the use of a metalloligand design strategy and a judicious choice of ligands inspired from nature is a versatile approach to succeed in this challenging task. We report a new porous chiral MOF, with the formula Ca 5 II {Cu II 10 [( S , S )-aspartamox] 5 }·160H 2 O ( 1 ), constructed from Cu 2+ and Ca 2+ ions and aspartic acid-decorated ligands, where biometal Cu 2+ ions are bridged by the carboxylate groups of aspartic acid moieties. The structure of MOF 1 reveals an infinite network of basket-like cages, built by 10 crystallographically distinct Cu(II) metal ions and five aspartamox ligands acting as bricks of a tubular motif, composed of seven basket-like cages each. The pillared hepta-packed cages generate pseudo-rhombohedral nanosized channels of ca. 0.7 and 0.4 nm along the b and a crystallographic axes. This intricate porous 3D network is anionic and chiral, each cage displaying receptor properties toward three-nuclear [Ca 3 (μ-H 2 O) 4 (H 2 O) 17 ] 6+ entities. 1 represents the first example of an extended porous structure based on essential biometals Cu 2+ and Ca 2+ ions together with aspartic acid as amino acid. 1 shows good biocompatibility, making it a good candidate to be used as a drug carrier, and hydrolyzes in acid water. The hypothesis has been further supported by an adsorption experiment here reported, as a proof-of-principle study, using dopamine hydrochloride as a model drug to follow the encapsulation process. Results validate the potential ability of 1 to act as a drug carrier. Thus, these make this MOF one of the few examples of biocompatible and degradable porous solid carriers for eventual release of drugs in the stomach stimulated by gastric low pH.

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

Cited by 6 publications

References 29 publications

Inclusion Polymerization of Pyrrole and Ethylenedioxythiophene in Assembled Triphenylamine Bis-Urea Macrocycles

Inclusion Polymerization of Pyrrole and Ethylenedioxythiophene in Assembled Triphenylamine Bis-Urea Macrocycles

Cyclodextrin metal–organic frameworks and derivatives: recent developments and applications

A Biocompatible Aspartic-Decorated Metal–Organic Framework with Tubular Motif Degradable under Physiological Conditions

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