A Redox-Active Bistable Molecular Switch Mounted inside a Metal–Organic Framework

Chen, Qishui; Sun, Jiazeng; Li, Peng; Hod, Idan; Moghadam, Peyman Z.; Kean, Zachary S.; Snurr, Randall Q.; Hupp, Joseph T.; Farha, Omar K.; Stoddart, J. Fraser

doi:10.1021/jacs.6b09880

Cited by 119 publications

(106 citation statements)

References 55 publications

(40 reference statements)

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“…These rings can be controllably rotated relative to one another through redox‐active functional groups. Additionally, the presence of weak interactions, such as hydrogen bonding in each of the two states, often results in changes in chemical and physical properties …”

Section: Mof Switching With Redoxmentioning

confidence: 99%

Switching in Metal–Organic Frameworks

et al. 2019

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In recent years, metal–organic frameworks (MOFs) have become an area of intense research interest because of their adjustable pores and nearly limitless structural diversity deriving from the design of different organic linkers and metal structural building units (SBUs). Among the recent great challenges for scientists include switchable MOFs and their corresponding applications. Switchable MOFs are a type of smart material that undergo distinct, reversible, chemical changes in their structure upon exposure to external stimuli, yielding interesting technological applicability. Although the process of switching shares similarities with flexibility, very limited studies have been devoted specifically to switching, while a fairly large amount of research and a number of Reviews have covered flexibility in MOFs. This Review focuses on the properties and general design of switchable MOFs. The switching activity has been delineated based on the cause of the switching: light, spin crossover (SCO), redox, temperature, and wettability.

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Section: Mof Switching With Redoxmentioning

confidence: 99%

Switching in Metal–Organic Frameworks

et al. 2019

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“…Redox processes related to the gain and loss of electrons are very common in nature and have been employed to build assorted electroactive materials for various technological applications. Several examples of redox‐responsive OMS incorporated into MOFs have also been reported . For example, Dincaˇ and co‐workers synthesized NDI‐based redox active organic linkers to build Zn(NDI‐X) (X = H, SEt, NHEt) MOF thin films on fluorine‐doped tin oxide (FTO)‐coated glass substrates .…”

Section: Switching Behaviors Of Immobilized Oms In Mofsmentioning

confidence: 99%

“…Recently, by using a postsynthetic solvent‐assisted ligand incorporation (SALI) method, Stoddart and co‐workers successfully incorporated MIMs‐based switches into a robust zirconium‐based MOF (NU‐1000, Figure ) . For example, A semirotaxane consisted of a viologen‐containing thread and a tetracationic cyclobis(paraquat‐ p ‐phenylene) macrocycle was incorporated in activated NU‐1000 through coordination in an inert atmosphere .…”

Section: Switching Behaviors Of Immobilized Oms In Mofsmentioning

confidence: 99%

“…For example, A semirotaxane consisted of a viologen‐containing thread and a tetracationic cyclobis(paraquat‐ p ‐phenylene) macrocycle was incorporated in activated NU‐1000 through coordination in an inert atmosphere . Later on, they reported the immobilization of bistable [2]catenane‐based molecular switches into NU‐1000 again by the SALI method (Figure ) . Cyclic voltammetry characterizations were performed on bistable [2]catenane‐functionalized NU‐1000 thin films to prove that the reversibly redox‐switchable molecular circumrotations of MIMs can be maintained in the solid state.…”

Section: Switching Behaviors Of Immobilized Oms In Mofsmentioning

confidence: 99%

Section: Switching Behaviors Of Immobilized Oms In Mofsmentioning

confidence: 99%

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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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MIMs in MOFs: Designing Mechanically Interlocked Molecules to Function Inside Metal–Organic Frameworks

Wilson,

Loeb

2024

Mechanically Interlocked Materials

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A Redox-Active Bistable Molecular Switch Mounted inside a Metal–Organic Framework

Cited by 119 publications

References 55 publications

Switching in Metal–Organic Frameworks

Switching in Metal–Organic Frameworks

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

MIMs in MOFs: Designing Mechanically Interlocked Molecules to Function Inside Metal–Organic Frameworks

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