Mechanically Interlocked Linkers inside Metal–Organic Frameworks: Effect of Ring Size on Rotational Dynamics

Vukotic, V. Nicholas; O’Keefe, Christopher A.; Zhu, Kelong; Harris, Kristopher J.; To, Christine; Schurko, Robert W.; Loeb, Stephen J.

doi:10.1021/jacs.5b04674

Cited by 100 publications

(94 citation statements)

References 87 publications

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“…90d This was followed by studies showing the effects upon rotation of changing the size and type of macrocycle. 91 Recent studies have shown that this type of thermally driven motion can also be induced inside a Zn II MORF in which the thread is an imidazolium ion (Fig 24b). 92 Interestingly, it was also demonstrated, using a rotaxane pillared (Fig 24c) The concept of arraying switchable MIMs within an ordered network is an attractive extension of these polymeric systems that has begun to be explored, 94 offering the potential advantage of addressing the interlocked components individually.…”

Section: Mim Coordination Polymers With Dynamic Componentsmentioning

confidence: 90%

“…91 In 2012, Loeb and co-workers prepared the first MORF (UWDM-1) with a rotaxane linker that showed large amplitude motion of one of the components in the solid state (Fig 24a). Using an aniline-based thread and a crown ether macrocycle labelled with deuterium atoms it was demonstrated using variable temperature (VT) 2 H solid-state (SS) NMR that the macrocyclic ring was free to undergo rotation about the coordination polymer backbone.…”

Section: Mim Coordination Polymers With Dynamic Componentsmentioning

confidence: 99%

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Metal ions in the synthesis of interlocked molecules and materials

et al. 2017

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The use of metal ions to template the synthesis of catenanes by Sauvage and co-workers was a pivotal moment in the development of the field of interlocked molecules. In this Review Article we shall examine the different roles metal-ligand interactions play in modern syntheses of interlocked molecules and materials, with a particular focus on seminal contributions and the advantages and disadvantages of employing metal ligand interactions.

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Section: Mim Coordination Polymers With Dynamic Componentsmentioning

confidence: 90%

Section: Mim Coordination Polymers With Dynamic Componentsmentioning

confidence: 99%

Metal ions in the synthesis of interlocked molecules and materials

et al. 2017

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“…In addition to the stimuli‐responsive MOFs summarized above, there are also unique “robust dynamic” systems showing dynamic properties of MIMs in the MOFs. Until now, only a few examples have been reported . The pioneering work showing dynamic motions of rotaxanes ( Figure A) in an MOF was reported by Loeb and his co‐workers .…”

Section: Switching Behaviors Of Immobilized Oms In Mofsmentioning

confidence: 99%

“…Until now, only a few examples have been reported. [85][86][87][88] The pioneering work showing dynamic motions of rotaxanes ( Figure 6A) in an MOF was reported by Loeb and his co-workers. [85] Starting from a [2]rotxane-based organic linker and Cu(NO 3 ) 2 , an MIM-based MOF (UWDM-1) was obtained.…”

Section: Robust Dynamics 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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“…Over the past two decades, a series of supramolecular coordination complexes with well define shapes have been prepared owing to their interesting structural features and potential applications in molecular recognition, drug delivery, catalytic, chemical sensors, host−guest chemistry and so on. [1][2][3][4][5][6][7][8][9][10][11] A large number of macrocyclic or cage structures have been obtained by rationally designed metal directional self-assembly approach. Especially, favorable host-guest properties of metallacycles and metallacages have gained by organic linkers.…”

Section: Introductionmentioning

confidence: 99%

Coordination‐driven self‐assembly of Cp*Rh‐Based Rectangles, Cages and Their Host−Guest Binding Study

Lin

Jin

2019

Applied Organom Chemis

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Supramolecular coordination‐driven self‐assembly rectangle 1a have be formation of distorted shapes, with a strong π···π interactions between the L1 and anthracene in 1b (1a ⊃ anthracene) that changed the size to desired and supported by single‐crystal Xray diffraction data. The formation of 1c(1a ⊃ DMF) has been further corroborated by the single‐crystal and 1b also can reaction with decaborane to form ortho‐carborane complex 1d. A self‐assembled triangular prism cage 2a consisting of binuclear half‐sandwich metal precursors [Cp*2Rh2(μ‐BiBzIm)]Cl2 (BiBzIm = 2,2′‐bisbenzimidazole) ligands and L2 were found to capsulated a triphenylene in cage. Another two kinds of prismatic cages (3a and 3b) were obtained from the reactions of the bis‐chelating‐coordinated [Cp*2Rh2(μ‐CA)]Cl2(CA = chloranilate) with L2 and L3 in the presence of AgOTf (OTf = CF3SO3) in CH3OH, and cage 3b have a perfect sized cavity to self‐assembled with anthracene in it.

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Mechanically Interlocked Linkers inside Metal–Organic Frameworks: Effect of Ring Size on Rotational Dynamics

Cited by 100 publications

References 87 publications

Metal ions in the synthesis of interlocked molecules and materials

Metal ions in the synthesis of interlocked molecules and materials

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

Coordination‐driven self‐assembly of Cp*Rh‐Based Rectangles, Cages and Their Host−Guest Binding Study

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