Mechanische Stabilität versus ultrahohe Porosität in kristallinen Netzwerkmaterialien: ein Balanceakt!

Hönicke, Ines M.; Senkovska, Irena; Bon, Volodymyr; Baburin, Igor A.; Bönisch, Nadine; Raschke, Silvia; Evans, Jack D.; Kaskel, Stefan

doi:10.1002/ange.201808240

Cited by 27 publications

(5 citation statements)

References 47 publications

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“…By employing strong and directional coordination bonds between the building blocks, permanently porous MOF glasses with interconnected micropores that are accessible to guest molecules can be made as monoliths, [6] making them useful for gas storage and separations, [7–9] sensing, [10] energy storage, [11] and catalysis [4] . Although previous reports demonstrated MOF glasses with permanent porosity, their N 2 Brunauer–Emmett–Teller (BET) surface areas were only on the order of 100 m 2 g −1 , [6] which is at least one order of magnitude lower than their crystalline counterparts [12–14] . A higher porosity would be required to harness the full potential of MOF glasses, which is impeded by their weak connectivity, thus making their pores architecturally frail.…”

Section: Figurementioning

confidence: 97%

High‐Porosity Metal‐Organic Framework Glasses

Hanikel

Lomachenko

et al. 2023

Angew Chem Int Ed

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We report a synthetic strategy to link titanium-oxo (Ti-oxo) clusters into metal-organic framework (MOF) glasses with high porosity though the carboxylate linkage. A new series of MOF glasses was synthesized by evaporation of solution containing Tioxo clusters Ti 16 O 16 (OEt) 32 , linkers, and m-cresol. The formation of carboxylate linkages between the Ti-oxo clusters and the carboxylate linkers was confirmed by Fourier-transform infrared (FT-IR) spectroscopy. The structural integrity of the Ti-oxo clusters within the glasses was evidenced by both X-ray absorption near edge structure (XANES) and 17 O magic-angle spinning (MAS) NMR. After ligand exchange and activation, the fumarate-linked MOF glass, termed Ti-Fum, showed a N 2 Brunauer-Emmett-Teller (BET) surface areas of 923 m 2 g À 1 , nearly three times as high as the phenolatelinked MOF glass with the highest BET surface area prior to this report.

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Section: Figurementioning

confidence: 97%

High‐Porosity Metal‐Organic Framework Glasses

Hanikel

Lomachenko

et al. 2023

Angew Chem Int Ed

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“…Thus, we hypothesize that void pre‐organization could promote hydrazone isomerization and advance efficient switching in the solid state [55, 56] . Well‐defined porous materials such as metal‐organic and covalent‐organic frameworks (MOFs and COFs) [57–77] offer such space for isomerization to occur, and therefore, can be used to promote photochromic performance of hydrazone derivatives. Indeed, herein we demonstrated the realization of this concept for the first time using hydrazone derivatives with light‐induced switching which are coordinatively‐immobilized within porous MOF and COF scaffolds.…”

Section: Introductionmentioning

confidence: 99%

Confinement‐Driven Photophysics in Hydrazone‐Based Hierarchical Materials

et al. 2022

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Confinement‐imposed photophysics was probed for novel stimuli‐responsive hydrazone‐based compounds demonstrating a conceptual difference in their behavior within 2D versus 3D porous matrices for the first time. The challenges associated with photoswitch isomerization arising from host interactions with photochromic compounds in 2D scaffolds could be overcome in 3D materials. Solution‐like photoisomerization rate constants were realized for sterically demanding hydrazone derivatives in the solid state through their coordinative immobilization in 3D scaffolds. According to steady‐state and time‐resolved photophysical measurements and theoretical modeling, this approach provides access to hydrazone‐based materials with fast photoisomerization kinetics in the solid state. Fast isomerization of integrated hydrazone derivatives allows for probing and tailoring resonance energy transfer (ET) processes as a function of excitation wavelength, providing a novel pathway for ET modulation.

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“…Metal-organic frameworks (MOFs) are microporous compounds that can reach very high surface areas of over 7000 m 2 /g. [1][2][3] The majority of MOFs in the literature are synthesized using derivatives of arylcarboxylic acid linkers. [4][5][6][7][8][9][10] Traditional arylcarboxylate MOFs often contain well-defined molecular inorganic building units (IBUs) such as paddle wheel patterns.…”

Section: Introductionmentioning

confidence: 99%

High Electrical Conductivity in Three-Dimensional Porphyrin-Phosphonate Metal Organic-Frameworks

Zorlu¹,

Tholen²,

Ayhan³

et al. 2021

Preprint

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Herein, we report the design and synthesis of a highly electrically conductive and microporous three-dimensional zinc-phosphonate metal-organic framework [Zn(Cu-p-H4TPPA)] ⋅2 (CH3)2NH2+ (designated as GTUB3), constructed using the 5,10,15,20‐tetrakis [p‐phenylphosphonic acid] porphyrin (p-H8TPPA) organic linker. GTUB3 has an indirect band gap of 1.64 eV and a high average electrical conductivity of 4 S/m, making it a rare example of an electrically conductive zinc metal-organic framework. The N2-accessible geometric surface area of GTUB3, as predicted by molecular simulations, is 671 m2/g. Owing to its simple, high-yield synthesis at low temperatures, porosity, and electrical conductivity, GTUB3 may be used as a low-cost electrode material in next generation phosphonate-supercapacitors.

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Mechanische Stabilität versus ultrahohe Porosität in kristallinen Netzwerkmaterialien: ein Balanceakt!

Cited by 27 publications

References 47 publications

High‐Porosity Metal‐Organic Framework Glasses

High‐Porosity Metal‐Organic Framework Glasses

Confinement‐Driven Photophysics in Hydrazone‐Based Hierarchical Materials

High Electrical Conductivity in Three-Dimensional Porphyrin-Phosphonate Metal Organic-Frameworks

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