Frontispiece: Magnetic Control of MOF Crystal Orientation and Alignment

Cheng, Fei; Marshall, Ellis S.; Young, Adam J.; Robinson, Peter; Bouillard, Jean-Sébastien; Adawi, Ali M.; Vermeulen, Nicolaas A.; Farha, Omar K.; Reithofer, Michael R.; Chin, Jia Min

doi:10.1002/chem.201786263

Cited by 3 publications

(7 citation statements)

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“…Nevertheless, magnetic fields can be easily applied across macroscopic areas to form centimeter scale structures with oriented MOFs. [ 145 ] In contrast, E‐fields can be directly applied to as‐synthesized MOF crystals, without the need for post‐synthetic modification. However, the generation of sufficiently strong E‐fields across large areas requires cumbersome set‐ups and entails safety concerns due to the high voltages required.…”

Section: Discussionmentioning

confidence: 99%

“…To bypass this limitation, Cheng et al. [ 145 ] focused on a general method to magnetize rod or needle‐shaped MOF crystals by exploiting electrostatic attractions between the MOFs and oppositely charged Fe 3 O 4 nanoparticles to attach the Fe 3 O 4 onto the external crystal surfaces of the MOFs. The zeta potentials of colloidal particles in aqueous media depend upon the pH of the dispersion – two types of particles in a colloidal dispersion can thereby be rendered oppositely charged by selecting a pH in between their isoelectric points.…”

Section: Oriented Polycrystalline Mof Superstructures By External Forcesmentioning

confidence: 99%

“…The versatility of this approach was demonstrated by aligning Fe 3 O 4 ‐coated NU‐1000 with AR = 5.9. [ 145 ] NU‐1000 exhibits unique optical properties along the c ‐crystallographic axis. Thus, its fluorescence response to 405 nm linearly polarized radiation when magnetically aligned was investigated showing different behaviors with respect to the unaligned NU‐1000.…”

Section: Oriented Polycrystalline Mof Superstructures By External Forcesmentioning

confidence: 99%

“…[ 66,144 ] The second method we will examine uses external forces (e.g., external electromagnetic field) to align pre‐formed anisotropic MOF crystals suspended in a solvent (see Figure 6b and Video S3, Supporting Information). [ 82,86,145 ] The third and last approach we will describe is a specific ceramic‐to‐MOF conversion; via heteroepitaxial growth, this wet approach enables the fabrication of 3D‐oriented MOF crystals in the centimeter range (see Figure 6c and Video S4, Supporting Information). At the moment, these methods are in their infancy and we posit that further progress is needed to unlock their full potential.…”

Section: Introductionmentioning

confidence: 99%

“…Adapted with permission. [ 145 ] Copyright 2017, John Wiley and Sons. (c) Schematic illustration of the electric‐field‐assisted (E‐field assisted) assembly of rhombic dodecahedra‐shaped ZIF‐8 crystals (sodalite ZIF‐8).…”

Section: Introductionmentioning

confidence: 99%

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Fabrication of Oriented Polycrystalline MOF Superstructures

Linares‐Moreau,

Brandner,

Velásquez‐Hernández

et al. 2023

Advanced Materials

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The field of metal‐organic frameworks (MOFs) has progressed beyond the design and exploration of powdery and single‐crystalline materials. A current challenge is the fabrication of organized superstructures that can harness the directional properties of the individual constituent MOF crystals. To date, the progress in the fabrication methods of polycrystalline MOF superstructures has led to close‐packed structures with defined crystalline orientation. By controlling the crystalline orientation, the MOF pore channels of the constituent crystals can be aligned along specific directions: these systems possess anisotropic properties including enhanced diffusion along specific directions, preferential orientation of guest species, and protection of functional guests. In this perspective, we discuss the current status of MOF research in the fabrication of oriented polycrystalline superstructures focusing on the specific crystalline directions of orientation. Three methods are examined in detail: the assembly from colloidal MOF solutions, the use of external fields for the alignment of MOF particles, and the heteroepitaxial ceramic‐to‐MOF growth. This perspective aims at promoting the progress of this field of research and inspiring the development of new protocols for the preparation of MOF systems with oriented pore channels, to enable advanced MOF‐based devices with anisotropic properties.

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Section: Discussionmentioning

confidence: 99%

Section: Oriented Polycrystalline Mof Superstructures By External Forcesmentioning

confidence: 99%

Section: Oriented Polycrystalline Mof Superstructures By External Forcesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Fabrication of Oriented Polycrystalline MOF Superstructures

Linares‐Moreau,

Brandner,

Velásquez‐Hernández

et al. 2023

Advanced Materials

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Synchronous Electrochromism and Electrofluorochromism in a Zirconium Pyrenetetrabenzoate Metal–Organic Framework

Guerraf,

Zeng,

Mantel

et al. 2024

Adv Elect Materials

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Redox‐active materials that exhibit both electrochromism and electrofluorochromism have great potential as multifunctional elements in optoelectronics. Here, in situ spectroelectrochemistry is presented on NU‐1000, a zirconium pyrenetetrabenzoate metal–organic framework. A thin film of NU‐1000 exhibits reversible color changes between light yellow and dark blue when subjected to an alternating electrochemical potential. In situ fluorescence excitation‐emission spectral mapping elucidates a dominant blue emission of highly fluorescent electrochromic NU‐1000 that is being quenched via an oxidation reaction. Density‐functional theory calculations reveal the forbidden optical transition between the singly occupied molecular orbital (SOMO) and the lowest unoccupied molecular orbital (LUMO) in the oxidized linker as the cause of the quenching. Double potential step chronoamperometry measures response times as fast as a dozen seconds and excellent switching stability over 500 cycles without noticeable attenuation of the color contrast. These findings provide valuable insight into the electrochromism and electrofluorochromism in metal–organic frameworks, offering exciting opportunities for developing advanced multifunctional porous materials with potential applications in optoelectronics and sensing.

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Synchronous electrochromism and electrofluorochromism in a zirconium pyrenetetrabenzoate metal-organic framework

El Guerraf,

Zeng,

Mantel

et al. 2023

Preprint

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Redox-active materials which exhibit both electrochromism and electrofluorochromism have great potential as multifunctional elements in optoelectronics. Here we present in situ spectroelectrochemistry on NU-1000, a zirconium pyrenetetrabenzoate metal-organic framework. A thin film of NU-1000 exhibits reversible color changes between light yellow and dark blue when subjected to an alternating electrochemical potential. In situ fluorescence excitation-emission spectral mapping elucidates a dominant blue emission of highly fluorescent electrochromic NU-1000 that is being quenched via an oxidation reaction. Density-functional theory calculations reveal the the forbidden optical transition between the singly-occupied molecular orbital (SOMO) and the lowest unoccupied molecular orbital (LUMO) in the oxidized linker as the cause of the quenching. Double potential step chronoamperometry meaures response times as fast as a dozen seconds and excellent switching stability over 500 cycles without noticeable attenuation of the color contrast. These findings provide valuable insight into the electrochromism and electrofluorochromism in metal-organic frameworks, offering exciting opportunities for developing advanced multifunctional porous materials with potential applications in optoelectronics and sensing.

show abstract

Frontispiece: Magnetic Control of MOF Crystal Orientation and Alignment

Cited by 3 publications

References 0 publications

Fabrication of Oriented Polycrystalline MOF Superstructures

Fabrication of Oriented Polycrystalline MOF Superstructures

Synchronous Electrochromism and Electrofluorochromism in a Zirconium Pyrenetetrabenzoate Metal–Organic Framework

Synchronous electrochromism and electrofluorochromism in a zirconium pyrenetetrabenzoate metal-organic framework

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