Stepwise crystallographic visualization of dynamic guest binding in a nanoporous framework

Brunet, Gabriel; Safin, Damir A.; Aghaji, Mohammad Zein; Robeyns, Koen; Korobkov, Ilia; Woo, Tom K.; Murugesu, Muralee

doi:10.1039/c7sc00267j

Cited by 70 publications

(54 citation statements)

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“…Furthermore,w ec orrelate this phenomenon to the structural reorganization of the host framework, elucidating the dynamic interplay between the container and the content [34,43] (Figure 2a). To deeply understand the physiology of PUM168 breathing during the guest uptake,w ef ocused our attention on the three main actors involved in the play: 1) the MOF structure;2)the DMF molecules trapped during the synthesis of the MOF;a nd 3) the incoming eugenol molecules.The fate of each actor influences and is influenced by the other two characters,i naplay that shows how the structure of the framework changes in response to the change of the guest composition (Figure 2b).…”

Section: Introductionmentioning

confidence: 98%

“…[36,37] Recent works have shown that cutting-edge use of SCXRD allows the elucidation of inclusion processes occurring inside MOF cavities based on structural insight. [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%

“…[27][28][29] However,i ns everal cases,t he determination of the guest species remains av ery demanding task [4] owing to the weak host-guest intermolecular interactions,mainly H-bonds, halogen-bonds,o rp-p interactions very often characterized by as ignificant positional disorder, [30] large thermal motion, and low occupancy. [4] Even though several works focusing on CSM have been presented so far, [18,19,[31][32][33] the analysis of the guest entering dynamics has not been explicitly investigated, [21,34,35] nor the formation of nanoconfined aggregates of the trapped molecules. [36,37] Recent works have shown that cutting-edge use of SCXRD allows the elucidation of inclusion processes occurring inside MOF cavities based on structural insight.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2019

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“…The I1-I 2d istance equals 2.73(2) , which is comparable to the I-I separations reported in other crystal structures ( Figure S5, Supporting Information) and our DFT-computed value (2.688 ). The I 2 molecule is nearly perpendicular to one pyrene core of TBAPy 4À and nearly parallel to the neighboring one with the shortest I 2 ···TBAPy 4À distance of 3.609 (15) (Figure 1b). Visualization of the crystal structure of SION-8'I 2 may suggest the existence of infinite (ÀIÀIÀ) n chains;h owever,c onsidering that the I1 and I2 atom sites are not fully occupied, such chains are probably not formed.…”

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confidence: 99%

Incarceration of Iodine in a Pyrene‐Based Metal–Organic Framework

Gładysiak

Nguyen

Spodaryk

et al. 2018

Chemistry A European J

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Ap yrene-based metal-organic framework (MOF) SION-8 captured iodine (I 2 )v apor with ac apacity of 460 and 250 mg g À1 MOF at room temperature and 75 8C, respectively.S ingle-crystal X-ray diffraction analysisa nd van-der-Waals-correctedd ensity functional theory calculations confirmed the presence of I 2 molecules within the pores of SION-8 and their interaction with the pyrene-based ligands.T he I 2 -pyrene interactions in the I 2 -loaded SION-8 led to a1 0 4 -fold increase of its electrical conductivity compared to the bare SION-8.U pon adsorption, ! 95 %o fI 2 molecules were incarcerated and could not be washed out, signifying the potentialofSION-8 towardst he permanent capture of radioactiveI 2 at room temperature.Radioactivei sotopes of iodine, mainly 129 Ia nd 131 I, are produced in nuclear-related processes and maya ccidentally be released into the atmosphere, as witnessed in Fukushima and Chernobyl,c onstituting am ajor hazard to humans and the environment. Isotope 131 Ih as ar adioactive decay half-life of about eight days, emits b À and g rays, and concentrates in the thyroid gland of the person exposed to the radioactive source causing thyroidc ancer.T he 129 Ii sotope has am uch longerl ife, with ah alf-lifeo f1 5.7 million years, and poses al ong-term disposalr isk. Capturing radioactive iodine is therefore necessary for safe nuclear wastes torage. [1] Wet scrubbing and the use of solid adsorbentsa re two general methodsf or iodine capture, with the latter being often preferred because it does not require the use of highly corrosive liquids. [1] The benchmark solid adsorbents for radioactive iodinec apture is thes ilver (Ag)-exchanged zeolitic mordenite, with an average I 2 -adsorption capacityo fa pproximately 100-130 mg g À1 mordernite at high temperatures (150-200 8C). [1, 2] In recenty ears, metal-organic frameworks (MOFs), which are crystalline materials formed by linkingm etal ions or metal clusters with multi-topic organic ligands, [3] have emergeda sp romising adsorbents for I 2 captured ue to their high porosity [4] and chemicaltunability. [5] For example, our group has previouslyreportedahigh I 2 vapor uptake by HKUST-1 and ZIF-8,a nd their composites with polymers, reaching 538 mg g À1HKUST-1 at 75 8C.[6] The Nenoff group and the Thallapally group have studied the adsorption of I 2 on HKUST-1a nd SBMOFs, respectively,i nt he presence of humidity. [7] However,t he degradation of these MOFs in water,a nd the leaching of I 2 from the I 2 -loaded MOFs when they are in contact with water and common organic solvents,g ive rise to considerable concerns regarding the potential of theseM OFs for I 2 capture. The I 2 leachingi st hought to be due to the weak interaction between the I 2 molecules with the pore surface of the MOF.Here, we report aM OF named SION-8,w hich is based on the employment of 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H 4 TBAPy)a nd Ca II , [8] that can efficientlyc aptureI 2 vapor at both room temperature and at 75 8C. The strategy for I 2 capture is based on the well-know...

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“…However, in several cases, the determination of the guest species remains a very demanding task owing to the weak host–guest intermolecular interactions, mainly H‐bonds, halogen‐bonds, or π–π interactions very often characterized by a significant positional disorder, large thermal motion, and low occupancy . Even though several works focusing on CSM have been presented so far, the analysis of the guest entering dynamics has not been explicitly investigated, nor the formation of nanoconfined aggregates of the trapped molecules …”

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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Stepwise crystallographic visualization of dynamic guest binding in a nanoporous framework

Abstract: The dynamic uptake behaviour of a gaseous guest has been observed crystallographically, yielding a unique and ever-changing set of host–guest interactions that will drive the improvement of high-capacity iodine capture materials.

Cited by 70 publications

References 45 publications

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

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

Incarceration of Iodine in a Pyrene‐Based Metal–Organic Framework

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

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