Direct Observation of Confined I−⋅⋅⋅I2⋅⋅⋅I− Interactions in a Metal–Organic Framework: Iodine Capture and Sensing

Hu, Yue; Li, Mu-Qing; Wang, Yanyan; Zhang, Tao; Liao, Pei‐Qin; Zheng, Zhiping; Chen, Xiaoming; Zheng, Yan‐Zhen

doi:10.1002/chem.201702087

Cited by 74 publications

(45 citation statements)

References 37 publications

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“…The environmental relevance of toxic gas capture and the electric conductivity enhancement caused by iodine uptake, have raised great interest on the incorporation of dihalogen molecules in diverse hosts like clathrasils,, zeosils,, and ALPOs, but also organic salts, organic zeolites, Hofmann clathrates,, and other MOFs …”

Section: Organization Of Dihalogens In 1d Channelsmentioning

confidence: 99%

Supramolecular Organization in Confined Nanospaces

Tabacchi

2018

ChemPhysChem

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Empty spaces are abhorred by nature, which immediately rushes in to fill the void. Humans have learnt pretty well how to make ordered empty nanocontainers, and to get useful products out of them. When such an order is imparted to molecules, new properties may appear, often yielding advanced applications. This review illustrates how the organized void space inherently present in various materials: zeolites, clathrates, mesoporous silica/organosilica, and metal organic frameworks (MOF), for example, can be exploited to create confined, organized, and self-assembled supramolecular structures of low dimensionality. Features of the confining matrices relevant to organization are presented with special focus on molecular-level aspects. Selected examples of confined supramolecular assemblies - from small molecules to quantum dots or luminescent species - are aimed to show the complexity and potential of this approach. Natural confinement (minerals) and hyperconfinement (high pressure) provide further opportunities to understand and master the atomistic-level interactions governing supramolecular organization under nanospace restrictions.

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Section: Organization Of Dihalogens In 1d Channelsmentioning

confidence: 99%

Supramolecular Organization in Confined Nanospaces

Tabacchi

2018

ChemPhysChem

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“…Similar phenomenon was observed for other I 2 @MOFs; for example, Hu et al. reported the MOF [Tb(Cu 4 I 4 )(ina) 3 (DMF)] in which the I 2 @[Tb(Cu 4 I 4 )(ina) 3 (DMF)] displayed a broad absorption over the visible window and its band gap was 1.5 eV lower than the one of the bare MOF . It is worth noting that the interaction of I 2 with aromatic compounds has been studied since the 1940s, and the hypothesis was that I 2 has an abnormally high dielectric polarization in these liquids and forms complexes of solvent–I + I − .…”

Section: Figurementioning

confidence: 99%

“…As can be observed in Figure , SION‐8⊃I 2 displays electrical conductivity ( σ ) that increases with increasing temperature and reaches σ =5.3×10 −6 S cm −1 at 23 °C. This value is comparable to those reported for other I 2 @MOFs, although the latter were obtained from a variety of different methods . An increase of electrical conductivity to a similar extent was also reported for other MOF charge‐transfer complexes, namely by utilizing fullerenes and TCNQ as electron acceptors .…”

Section: Figurementioning

confidence: 99%

“…Similar phenomenon was observed for other I 2 @MOFs;f or example, Hu et al reported the MOF [Tb(Cu 4 I 4 )(ina) 3 (DMF)] in which the I 2 @[Tb(Cu 4 I 4 )(ina) 3 (DMF)] displayed ab road absorption over the visible window and its band gap was 1.5 eV lower than the one of the bare MOF. [16] It is worth noting that the interaction of I 2 with aromatic compounds has been studied sincet he 1940s, and the hypothesis was that I 2 has an abnormally high dielectric polarization in these liquids and forms complexes of solvent-I + I À . [17] In the case of pyrene (and other highly aromatic compounds), the donor-acceptor charget ransfer between the pyrene molecule and I 2 leads to ah igh electrical conductivity of the pyrene-I 2 complex compared to its individual components.…”

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confidence: 99%

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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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“…Similar I 4 2ions were observed by Liao, Zheng and co-workers in a MOF containing Cu 4 I 4 nodes and isonicotinate ions, though no evidence of I 3ions was reported in this case. 30 While the interactions between [(ZnI 2 ) 3 (tpt) 2 ] and 1 with iodine are the only examples to date of absorption of iodine with concurrent conversion to I 3 -, previous papers have reported the direct uptake of triiodide from solution into a framework, [31][32] solvent triggered formation of triiodide from iodine within a framework, 33 and non-innocent redox processes triggered by iodine in a Fe 2+ framework. 34 A key advantage of the interaction described in this work is that the solution phase is by-passed in favor of harnessing reactivity at the gas/solid interface, which is desirable for materials and applications that target radioactive iodine vapor absorption.…”

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confidence: 99%

Evaluating Iodine Uptake in a Crystalline Sponge Using Dynamic X-ray Crystallography

et al. 2018

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The uptake of gaseous iodine into the crystalline sponge material [(ZnI)(tpt)]·0.7triphenylene·0.3PhNO·0.7CH 1 (tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine) has been monitored by dynamic X-ray diffraction and thermogravimetric analysis. The X-ray analyses have enabled the location, quantity, uptake rate, and subsequent chemistry of the iodine upon inclusion into the pores to be determined. An uptake of 6.0 wt % (0.43 I per formula unit) was observed crystallographically over a period of 90 min before crystal degradation occurred. The included iodine molecules interact with the iodine atoms of the ZnI nodes at three different sites, forming coordinated I ions. The results contrast to recent observations on [(ZnI)(tpt)] without the triphenylene guests which show the presence of I ions with low quantities of absorbed iodine.

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Direct Observation of Confined I⁻⋅⋅⋅I₂⋅⋅⋅I⁻ Interactions in a Metal–Organic Framework: Iodine Capture and Sensing

Cited by 74 publications

References 37 publications

Supramolecular Organization in Confined Nanospaces

Supramolecular Organization in Confined Nanospaces

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

Evaluating Iodine Uptake in a Crystalline Sponge Using Dynamic X-ray Crystallography

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