A series of entangled MOFs constructed from flexible dipyridyl piperazine and rigid dicarboxylate: interpenetration, self-penetration, and polycatenation

Ju, Huiyeong; Kim, Seulgi; Jung, Jong Hwa; Lee, Shim Sung

doi:10.1039/d2ce00745b

Cited by 4 publications

(4 citation statements)

References 75 publications

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“…Viewed from this perspective, the 2D wave-like subnets intertwine parallel to the direction of the nets to generate overall 2D arrays, which subsequently undergo supramolecular stacking to give rise to a 3D structure. It should be noted that the formation of porous frameworks based on this interpenetrated pattern of intertwining subnets is rare, while previously reported examples exhibited vertical or inclined interpenetration corresponding to the direction of the 2D nets. − The solvent-accessible volumes were determined by PLATON (with a probe radius of 1.2 Å) and found to be 43.4% and 42.7% for Flex-Cd-MOF-1 and Flex-Cd-MOF-2, respectively. , …”

Section: Resultsmentioning

confidence: 91%

Stimulus-Induced Dynamic Behavior Regulation of Flexible Crystals through the Tuning of Module Rigidity

Fang,

Liu,

Ding

et al. 2024

J. Am. Chem. Soc.

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Introducing dynamic behavior into periodic frameworks has borne fruit in the form of flexible porous crystals. The detailed molecular design of frameworks in order to control their collective dynamics is of particular interest, for example, to achieve stimulus-induced behavior. Herein, by varying the degree of rigidity of ditopic pillar linkers, two isostructural flexible metal−organic frameworks (MOFs) with common rigid supermolecular building bilayers were constructed. The subtle substitution of single (in bibenzyl-4,4′-dicarboxylic acid; H 2 BBDC) with double (in 4,4′stilbenedicarboxylic acid; H 2 SDC) C−C bonds in pillared linkers led to markedly different flexible behavior of these two MOFs. Upon the removal of guest molecules, both frameworks clearly show reversible single-crystal-tosingle-crystal transformations involving the cis−trans conformation change and a resulting swing of the corresponding pillar linkers, which gives rise to Flex-Cd-MOF-1a and Flex-Cd-MOF-2a, respectively. Strikingly, a more favorable gas-induced dynamic behavior in Flex-Cd-MOF-2a was verified in detail by stepwise C 3 H 6 /C 3 H 8 sorption isotherms and the corresponding in situ powder X-ray diffraction experiments. These insights are strongly supported by molecular modeling studies on the sorption mechanism that explores the sorption landscape. Furthermore, a consistency between the macroscopic elasticity and microscopic flexibility of Flex-Cd-MOF-2 was observed. This work fuels a growing interest in developing MOFs with desired chemomechanical functions and presents detailed insights into the origins of flexible MOFs.

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Section: Resultsmentioning

confidence: 91%

Stimulus-Induced Dynamic Behavior Regulation of Flexible Crystals through the Tuning of Module Rigidity

Fang,

Liu,

Ding

et al. 2024

J. Am. Chem. Soc.

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“…Indeed, DMA and DMF are frequently used in MOF constructions as a dipolar aprotic solvent medium with similar physical properties. In the MOF formations, some hypotheses for such a solvent effect rely on the relation of (i) the conformational variety of the linker ligands versus dimensionality and (ii) the entanglement (or clustering) versus guest size. − …”

Section: Resultsmentioning

confidence: 99%

Solvent-Dependent Zn(II) Supramolecular Isomers and [2 + 2] Photocycloaddition Reaction via an SCSC Transformation

Lee,

Oh,

et al. 2024

Crystal Growth & Design

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Each of the supramolecular isomerism and the solidstate [2 + 2] photocycloaddition has been developed as an independent research topic in crystal engineering. We herein report the solvent-dependent formations of the olefin-based supramolecular isomers (1 and 2) showing different photoreactivity. In the solvothermal reaction of Zn(NO 3 ) 2 •6H 2 O, 1,2-bis(4-pyridyl)ethylene (bpe), and 1-adamantanecarboxylic acid (Hadc) in dimethylacetamide(DMA)/water, we obtained a zigzag-shaped coordination polymer of the type [Zn(bpe)(adc) 2 ] (1). When dimethylformamide (DMF) was used instead of DMA, the railroad-shaped supramolecular isomer 2 was isolated. In 2, the dinuclear repeating units, Zn 2 (adc) 4 as railroad ties, are dilinked by bpe ligands. Under ultraviolet (UV) irradiation, isomer 1 was photoinert due to the large separation between the olefin (C�C) bonds in the bpe ligands. In contrast, isomer 2 was photoreactive because the olefin bonds of the parallel bpe linker ligands are well aligned in a face-to-face mode and separated by a distance of 3.79 Å to undergo [2 + 2] photocycloaddition quantitatively via an single-crystal-to-single-crystal (SCSC) manner. All of these products exhibit yellow emission in the 385−388 nm region with different intensities depending on the local structures.

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“…Entangled MOFs may have more abundant structures and unique properties. Through structural entanglement, MOFs could expand the surface area in the framework to improve the adsorption capacity, or divide large cavities into small space to maximize stacking efficiency, thus improving the thermal and chemical stability. , Interlocked MOF is a kind of entangled MOF to require the existence of closed rings in the chain . A long and curved organic ligand is usually selected to construct the interlocked MOF, which has easy to form large cavity structures .…”

Section: Introductionmentioning

confidence: 99%

“…30,31 Interlocked MOF is a kind of entangled MOF to require the existence of closed rings in the chain. 32 A long and curved organic ligand is usually selected to construct the interlocked MOF, which has easy to form large cavity structures. 31 Another organic ligand with fluorescent groups could be introduced to connect closed loops to enrich the structure of the interlocked MOF and enhance the luminescent properties.…”

Section: ■ Introductionmentioning

confidence: 99%

Multifunctional Fluorescence Turn-On Sensor for Acetylacetone, Glyoxal, and Salicylaldehyde Based on a Highly Stable 1D → 2D Interlocked Cd(II) Metal–Organic Framework

Zhang

Cai

et al. 2023

Crystal Growth & Design

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Metal−organic frameworks (MOFs) provide a broad platform for detecting small organic molecules due to their good stabilities and unique luminescent properties. Herein, a one-dimensional Cd II -based double chain metal−organic framework {[Cd(BBIP)(CDDB)(H 2 O)]•2H 2 O} n (JXUST-30) derived from 3,5-bis(1H-benzo[d]imidazol-1-yl)pyridine (BBIP) and 4,4′-(9H-carbazole-3,6-diyl)dibenzoic acid (H 2 CDDB) was successfully synthesized by solvothermal method. Interestingly, the Cd II −BBIP chain could pass through the large cavity formed by CDDB 2− to make parallel one-dimensional double chains interlocked, resulting in a structural transition from a one-dimensional chain to a twodimensional plane (1D → 2D) and the enhancement of structural stability. The intense blue light emission and the excellent stability in aqueous solutions with the wide range of pH values, organic solvents, and even boiling water of JXUST-30 provide a platform for detecting small organic molecules. The sensing experiments indicate that JXUST-30 can be used as a multifunctional fluorescence turn-on sensor for detecting acetylacetone (acac), aldehydes (glyoxal and salicylaldehyde (SA)) with fast response time (<15 s) and high sensitivity (detection limits of 0.068, 0.060, and 0.051 ppm, respectively). In addition, the successful preparation of sensing devices based on JXUST-30 provides the possibility for practical application in fluorescence detection of small organic molecules.

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A series of entangled MOFs constructed from flexible dipyridyl piperazine and rigid dicarboxylate: interpenetration, self-penetration, and polycatenation

Abstract: The initial evaluation for the MOF entanglements, the limitation, is changing to the opportunity since the related benefits have been known. Based on a linear rigid dicarboxylic acid, biphenyl-4,4’-dicarboxylic acid...

Cited by 4 publications

References 75 publications

Stimulus-Induced Dynamic Behavior Regulation of Flexible Crystals through the Tuning of Module Rigidity

Stimulus-Induced Dynamic Behavior Regulation of Flexible Crystals through the Tuning of Module Rigidity

Solvent-Dependent Zn(II) Supramolecular Isomers and [2 + 2] Photocycloaddition Reaction via an SCSC Transformation

Multifunctional Fluorescence Turn-On Sensor for Acetylacetone, Glyoxal, and Salicylaldehyde Based on a Highly Stable 1D → 2D Interlocked Cd(II) Metal–Organic Framework

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