Photoresponsive spiropyran-functionalised MOF-808: postsynthetic incorporation and light dependent gas adsorption properties

Healey, Katherine; Liang, Weibin; Southon, Peter D.; Church, Tamara L.; D’Alessandro, Deanna M.

doi:10.1039/c6ta04160d

Cited by 119 publications

(107 citation statements)

References 41 publications

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“…Our requirements for the platform MOF were that it should possess strong Lewis acidity and large pore size, and that it should be readily functionalised with the phosphine. After an initial screen through a series of reported early‐transition‐metal‐based Lewis acidic MOFs for their activity in imine formation (Table ), the large pore (1.8 nm) structure of MOF‐808(Zr) (Figure ), originally prepared as a zirconium 1,3,5‐benzene tricarboxylate, Zr 6 (μ 3 ‐O) 4 (μ 3 ‐OH) 4 (HCO 2 ) 6 ((O 2 C) 3 C 6 H 3 ) 6/3 seemed ideal, in the light of its high activity and the recent demonstration that formate groups on the secondary building units (SBUs) can be interchanged with other anions, such as carboxylates or sulfonates, by means of post‐synthetic modification . We speculated that it might be possible to conduct this exchange using known sulfonated phosphine ligands, the strong Zr−O bonds being expected to ensure that the cluster remains intact throughout the post‐synthetic modification.…”

Section: Resultsmentioning

confidence: 99%

“…After an initials creen throughaseries of reportede arly-transitionmetal-based Lewis acidic MOFs for their activity in imine formation( Ta ble 1), the large pore (1.8 nm) structure of MOF-808(Zr) [9] (Figure1), originally prepared as az irconium 1,3,5-benzene tricarboxylate, Zr 6 (m 3 -O) 4 (m 3 -OH) 4 (HCO 2 ) 6 ((O 2 C) 3 C 6 H 3 ) 6/3 seemed ideal, in the light of its high activity and the recent demonstrationt hat formate groups on the secondary building units (SBUs) can be interchanged with other anions, such as carboxylates or sulfonates, by means of post-synthetic modification. [10,11] We speculated that it might be possible to conduct this exchange using knowns ulfonated phosphine ligands, the strong ZrÀOb onds being expected to ensure that the cluster remains intact throughout the post-synthetic modification. Inspired by the higherL ewis acidityo fP CN-777(Hf) compared with its Zr analogue ( Table 1, entries 7a nd 8), the Hf version of MOF-808(Zr), MOF-808(Hf), was synthesised as micron-sized crystalsb yamethod similar to that subsequently reported by Liu et al [12] (Figure 2).…”

Section: Resultsmentioning

confidence: 99%

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A Bifunctional MOF Catalyst Containing Metal–Phosphine and Lewis Acidic Active Sites

Prasad

Dawson

Cox

et al. 2018

Chemistry A European J

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Post-synthetic modification of the hafnium metal-organic framework MOF-808(Hf) to include triarylphosphine ligands is reported. Sulfonated phenylphosphines are incorporated without oxidation to give a "MOF ligand" that can complex late transition metals such as Ir and Rh to give a bifunctional catalyst containing both metal-phosphine complexes and the Lewis acidic framework hafnium metal sites. The metallated phosphine-bearing MOFs act as fully heterogeneous bifunctional catalysts for tandem reductive amination and hydroaminomethylation reactions.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

A Bifunctional MOF Catalyst Containing Metal–Phosphine and Lewis Acidic Active Sites

Prasad

Dawson

Cox

et al. 2018

Chemistry A European J

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“…Spiropyrane wurden bereits früher unter Verwendung eines mikrowellenunterstützten Kristallisationseinschlussverfahrens in ein MOF (JUC-120) eingebaut, [61] aber auch postsynthetisch in MOF-808 eingeführt, indem Lçsungsmittel an besetzten Stellen an den Zr 6 -Knoten durch eine Vorstufe (1-(Carboxymethyl)-2,3,3-trimethyl-3H-indol-1-ium) ersetzt wurden und anschließend 2-Hydroxy-5-nitrobenzaldehyd zugegeben und damit kondensiert wurde,umdas spiropyrantragende MOF zu erhalten. [62] Schalten dieses Hilfsliganden unter Verwendung von sichtbarem oder UV-Licht modulierte die CO 2 -Aufnahme des Gerüsts.D as offene Spiropyranisomer wies eine deutlich hçhere CO 2 -Aufnahme auf als das geschlossene Isomer, was den Ladungen um die Stickstoffund Sauerstoffatome herum in der offenen Form zugeschrieben wurde,d ie eine grçßere Affinitätf ürC O 2 verursachen sollten.…”

Section: Mof-schaltung Mit Lichtunclassified

Schalten in Metall‐organischen Gerüsten

et al. 2019

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Aufgrund ihrer einstellbaren Poren und nahezu grenzenlosen Strukturdiversität, die sich aus dem Design verschiedener organischer Linker und metallischer Strukturbaueinheiten ableitet, haben sich Metall‐organische Gerüste (MOFs) in den vergangenen Jahren zu einem intensiv beforschten Gebiet entwickelt. Zu den größten Aufgaben gehören schaltbare MOFs und ihre Anwendung. Schaltbare MOFs sind “intelligente” Materialien, die bei Exposition gegenüber externen Stimuli eine deutliche, reversible, chemische Veränderung ihrer Struktur durchlaufen, was interessante technische Anwendungen ermöglicht. Obwohl dieser Prozess des Schaltens Ähnlichkeiten mit Flexibilität aufweist, haben sich nur sehr wenige Studien speziell mit Schalten beschäftigt, wohingegen sich eine recht große Zahl von Arbeiten und Übersichten mit der Flexibilität in MOFs beschäftigt. Dieser Aufsatz konzentriert sich auf die Eigenschaften und das allgemeine Design schaltbarer MOFs. Dabei wird die Schaltaktivität basierend auf der Ursache des Schaltens beschrieben: Licht, Spincrossover, Redoxchemie, Temperatur und Benetzbarkeit.

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“…Besides azobenzene and diarylethene, other photoresponsive molecules have also been immobilized into MOFs . For example, by using a two‐step postsynthetic modification method, D'Alessandro and co‐workers reported a spiropyran‐incorporated MOF, in which the spiropyran units can convert to the colored merocyanine state under UV irradiation. In addition, pyridinium‐ and naphthalenediimide (NDI)‐based functional units were also immobilized in MOFs to build photochromic porous materials.…”

Section: Switching Behaviors Of Immobilized Oms In Mofsmentioning

confidence: 99%

Immobilizing Organic‐Based Molecular Switches into Metal–Organic Frameworks: A Promising Strategy for Switching in Solid State

Gui

Meng

Xie

et al. 2017

Macromol. Rapid Commun.

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These organic-based molecular switches (OMS), [6][7][8][9][10] as their structures and functions can be efficiently tailored by synthetic methods based on centuries of knowledge in organic chemistry, are appealing components for constructing molecular devices, [11][12][13][14] nanoscale electronic circuits, [15][16][17] and various smart materials. [18][19][20][21] For further applications, in particular device fabrication, it is inevitable to incorporate OMS into various solid-state materials. [22][23][24][25] However, presumably because of spatial confinement or inefficient conversion in densely packed solid phase, [26,27] OMS in the solid state, which do not retain identical properties in solution, may partially or even completely lose their switchability and functionality.Immobilizing OMS into metal-organic frameworks (MOFs) ( Figure 1B), a class of organic-inorganic hybrids porous crystalline materials, [28][29][30][31][32][33] could provide a highly appealing route toward switching in solid state. For several reasons this approach is particularly attractive. First, the modularity of the organic components in MOFs paves the way for OMS to be incorporated either in the predesigned organic linkers [34,35] which latter employed as MOF building blocks or by postsynthetic modification approaches after MOF formation. [36] Second, the porosity offers both the essential space for the chemical reactants to access OMS in the MOF pores and appropriate room for OMS to change conformations in the solid-state. [37] Third, the robust nature of MOFs can allow the resulting OMS-based material maintain their crystallinity even upon drastic changes to some of their constituents. [38,39] With proper design strategies, the incorporation of OMS into MOFs not only provides unique opportunities for the solution characteristics of OMS to be smoothly reproduced in the solid state with high fidelity for further applications (e.g., memory device) but also allows the reversible single-crystal-to-singlecrystal transformations, which will enhance our fundamental understanding of the structure-function relationship for the designs and syntheses of novel stimuli-responsive materials.Over the past few years, a lot of efforts have been devoted to the construction of OMS-based MOFs. [40][41][42][43][44][45][46][47] Considering the increasing interest in this topic, we herein highlight the recent progress of stimuli-responsive MOFs with OMS inside as part of their organic components. In the first part, we discuss the switching behaviors of OMS under different stimuli in Stimuli-Responsive MaterialsOrganic-based molecular switches (OMS) are essential components for the ultimate miniaturization of nanoscale electronics and devices. For practical applications, it is often necessary for OMS to be incorporated into functional solid-state materials. However, the switching characteristics of OMS in solution are usually not transferrable to the solid state, presumably because of spatial confinement or inefficient conversion in densely packed solid pha...

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Photoresponsive spiropyran-functionalised MOF-808: postsynthetic incorporation and light dependent gas adsorption properties

Cited by 119 publications

References 41 publications

A Bifunctional MOF Catalyst Containing Metal–Phosphine and Lewis Acidic Active Sites

A Bifunctional MOF Catalyst Containing Metal–Phosphine and Lewis Acidic Active Sites

Schalten in Metall‐organischen Gerüsten

Immobilizing Organic‐Based Molecular Switches into Metal–Organic Frameworks: A Promising Strategy for Switching in Solid State

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